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Ruthenium(II)–Arene Complexes with Glycosylated NHC-Carbene Co-Ligands: Synthesis, Hydrolytic Behavior, and Binding to Biological Molecules
Electronic Supplementary Material (ESI) for Dalton Transactions.
This journal is © The Royal Society of Chemistry 2024
Supporting Information
The Coordination of Alkali-Metal Nickelates to Organic π-Systems:
Synthetic, Structural and Spectroscopic Insights
Andryj M. Borys,a* Luca Vedani,a Eva Heviaa*
a Departement für Chemie, Biochemie und Pharmacie, Universität Bern, 3012 Bern, Switzerland
Table of Contents
Experimental ............................................................................................................................................4
General Considerations ........................................................................................................................4
Synthesis and Purification of PhLi .........................................................................................................4
Synthesis of Alkali-Metal Nickelates ......................................................................................................5
Synthesis of [(ttt-CDT)NiPh][Li(12-crown-4)2] (1) ...............................................................................5
Synthesis of Li2(TMEDA)2Ph2Ni(η2-CDT) (2)......................................................................................5
Synthesis of Li4(TMEDA)2(Et2O)2Ph4Ni2(µ;η2;η2-C6H4) (3) ..................................................................6
Synthesis of Li2(THF)4Ph2Ni(η2-anthracene) (4Li)..............................................................................6
Synthesis of Na2(TMEDA)2Ph2Ni(η2-anthracene) (4Na) .....................................................................7
Synthesis of K2(PMDETA)2Ph2Ni(η2-anthracene) (4K) .......................................................................8
Synthesis of Li2(THF)4Ph2Ni(η2-phenanthrene) (5Li) .........................................................................8
Synthesis of [Na2(THF)3Ph2Ni(η2-phenanthrene)]2 (5Na) ...................................................................9
Synthesis of [K2(THF)1Ph2Ni(η2-phenanthrene)]∞ (5K) .....................................................................10
Synthesis of [Li(THF)2Ph2Ni(η3-perylene)][Li(THF)4] (6Li) ................................................................10
Synthesis of [Li(THF)2Ph2Ni(η2-coronene)][Li(THF)4] (7Li)...............................................................11
Synthesis of K2(DME)4Ph2Ni(η2-coronene) (7K) ..............................................................................11
Synthesis of [Li2(THF)3Ph2Ni(η2-Ph2CO)]2 (8Li) ...............................................................................12
Synthesis of [K2(DME)3Ph2Ni(η2-Ph2CO)]2 (8K) ...............................................................................12
Synthesis of Li2(THF)5Ph2Ni(η2-PhCH=NPh) (9Li) ...........................................................................13
Synthesis of [Li2(THF)3Ph2Ni(η2-Ph2CHCN)]2 (10Li) ........................................................................14
Synthesis of Li(THF)3(PPh3)2(CO)3Ni2(µ-PPh2) (11Li)......................................................................14
Variable Temperature NMR Spectroscopy .............................................................................................15
[Li(THF)2Ph2Ni(η2-coronene)][Li(THF)4] (7Li) ......................................................................................15
DOSY NMR Spectroscopy......................................................................................................................16
[Na2(THF)3Ph2Ni(η2-phenanthrene)]2 (5Na) .........................................................................................16
[K2(THF)1Ph2Ni(η2-phenanthrene)]∞ (5K).............................................................................................17
EPR Spectroscopy .................................................................................................................................18
X-Ray Crystallography............................................................................................................................20
Solid-State Structure of [(ttt-CDT)NiPh][Li(12-crown-4)2] (1) ...............................................................28
Solid-State Structure of Li4(TMEDA)2(Et2O)2Ph4Ni2(µ;η2;η2-C6H4) (3) ..................................................28
Solid-State Structure of Li2(THF)4Ph2Ni(η2-anthracene) (4Li) ..............................................................29
Solid-State Structure of Na2(TMEDA)2Ph2Ni(η2-anthracene) (4Na) .....................................................29
Solid-State Structure of K2(PMDETA)2Ph2Ni(η2-anthracene) (4K) .......................................................30
Solid-State Structure of Li2(THF)4Ph2Ni(η2-phenanthrene) (5Li) ..........................................................30
Solid-State Structure of [Na2(THF)3Ph2Ni(η2-phenanthrene)]2 (5Na) ...................................................31
Solid-State Structure of [K2(THF)1Ph2Ni(η2-phenanthrene)]∞ (5K) .......................................................31
Solid-State Structure of [Li(THF)2Ph2Ni(η3-perylene)][Li(THF)4] (6Li) ..................................................32
Solid-State Structure of [perylene][K(DME)4] .......................................................................................32
Solid-State Structure of [Li(THF)2Ph2Ni(η2-coronene)][Li(THF)4] (7Li) .................................................33
Solid-State Structure of K2(DME)4Ph2Ni(η2-coronene) (7K) .................................................................34
Solid-State Structure of [Li2(THF)3Ph2Ni(η2-Ph2CO)]2 (8Li) .................................................................34
Solid-State Structure of [K2(DME)3Ph2Ni(η2-Ph2CO)]2 (8K) .................................................................35
Solid-State Structure of Li2(THF)5Ph2Ni(η2-PhCH=NPh) (9Li) .............................................................36
Solid-State Structure of [Li2(THF)3Ph2Ni(η2-Ph2CHCN)]2 (10Li) ..........................................................36
Solid-State Structure of Li(THF)3(PPh3)2(CO)3Ni2(µ-PPh2) (11Li) ........................................................37
NMR Spectra of Reported Compounds ..................................................................................................38
Reference Spectra ..............................................................................................................................61
In Situ Synthesis and Characterisation of Imine Addition Product, Ph2CHN(Li)Ph ...........................64
In Situ Synthesis and Characterisation of Lithiated Diphenylketenimine, Ph2C=C=N–Li ..................66
References .............................................................................................................................................68
Experimental
General Considerations
All manipulations were carried out under an inert atmosphere of argon using standard Schlenk line or
glovebox techniques (MBraun UNILab Pro ECO, <0.1 ppm H2O and O2).1,2 All manipulations, except for
the synthesis of PhLi or Ni(ttt-CDT), must avoid the use of Teflon-coated stir bars or cannulae, and glasscoated stir bars should be used. THF was dried and distilled from Na/benzophenone and stored over 4 Å
molecular sieves, then further dried and vacuum distilled over NaK2.8 or a sodium mirror. Hexane, pentane,
Et2O and toluene were pre-dried using a MBraun MBSPS 5, then further dried and vacuum distilled over
NaK2.8 or a sodium mirror, and stored over 4 Å molecular sieves. THF-d8 and C6D6 were dried and vacuum
distilled over NaK2.8 and stored over 4 Å molecular sieves. TMEDA and PMDETA were distilled over CaH2
and stored over 4 Å molecular sieves. DME was dried and distilled from Na/benzophenone and stored
over 4 Å molecular sieves.12-crown-4 was degassed by three freeze-pump-thaw cycles and stored over
4 Å molecular sieves. Ni(ttt-CDT) was prepared according to literature procedures and purified by vacuum
sublimation.3 Anthracene and phenanthrene were dried and sublimed in vacuo prior to use. All other
reagents were used as supplied and dried in vacuo prior to use. Glovebox filtrations to separate insoluble
solids were performed using 0.2 µm polypropylene (PP) syringe filters. Low temperature glovebox
reactions were maintained using custom-made aluminium cooling blocks that were stored in the glovebox
freezer (-30 °C) prior to use.
NMR spectra were recorded on Bruker Avance III HD 300 MHz or 400 MHz spectrometers at 300 K unless
otherwise specified. 1H NMR spectra were referenced internally to the corresponding residual protio
solvent peaks. CHN elemental microanalyses were performed on a Flash 2000 Organic Elemental
Analyser (Thermo Scientific). Samples were prepared and crimped in tin capsules in an argon filled
glovebox. Analyses were performed in triplicate, and reference standards (e.g. nicotinamide) were
measured prior to use as controls. EPR spectra were recorded at room temperature in 1.5 mm inset
capillaries on a Bruker EMXnano instrument.
Synthesis and Purification of PhLi
Iodobenzene (10.7 mL, 96 mmol) was dissolved in hexane (200 mL) and cooled to -78 °C. nBuLi (1.6 M,
60 mL, 96 mmol) was added dropwise and the reaction was maintained at -78 °C for 30 minutes then
warmed to room temperature and stirred for 2 hours giving a thick colourless suspension. Additional
hexane (2 × 100 mL) was added to loosen the suspension, and the solids were collected on a filter frit,
then washed with hexane (2 × 50 mL), and dried in vacuo. Yield – 7.85 g (97%).
2.52 g of PhLi was suspended in hexane (40 mL) and Et2O (5 mL) was added. The cloudy solution was
filtered to remove insoluble impurities and the filtrate was stored at -40 °C for 3 hours to give colourless
crystals of [PhLi(Et2O)]4. The supernatant was removed via filter cannula and the crystals were thoroughly
dried in vacuo for several hours to remove coordinated Et2O. Yield – 2.15 g (84% recovery). 1H NMR
spectroscopy indicates 2% residual Et2O (MW = 85.52 g mol-1).
H NMR (300.1 MHz, THF-d8): δ 7.92 (m, 2H, o-CH), 6.85 (m, 2H, m-CH), 6.75 (m, 1H, p-CH).
1
Li NMR (116.6 MHz, THF-d8): δ 1.56 (s).
7
Analytical data in accordance with the literature.4
Synthesis of Alkali-Metal Nickelates
Synthesis of [(ttt-CDT)NiPh][Li(12-crown-4)2] (1)
Ni(ttt-CDT) (22.1 mg, 0.1 mmol) was dissolved in pre-cooled THF (0.5 mL) and cooled to -30 °C. PhLi (8.6
mg, 0.1 mmol) was slowly added as a pre-cooled solution in THF (0.5 mL) resulting in a colour change
from red to yellow. After stirring for 1 minute at -30 °C, 12-crown-4 (40 µL, 0.25 mmol) was added and the
solution was stirred for an additional minute before being filtered and stored at -30 °C for crystallisation via
pentane vapour diffusion. After 48 hours, the supernatant was decanted from the yellow crystals, which
were washed with cold pentane (2 × 0.5 mL) and dried under argon. Yield – 39 mg (59%).
H NMR (400.1 MHz, THF-d8, -20 °C): δ 7.72 (br, 2H, Ph-o-CH), 6.41 (br, 2H, Ph-m-CH), 6.20 (br, 1H, Ph-
1
p-CH), 3.39(s, 32H, 12-crown-4-CH2), 3.23 (br, 6H, CDT-CH2), 1.74 (br, 6H, CDT-CH2), 1.40 (br, 3H, CDTCH), 1.00 (br, 3H, CH).
Li NMR (155.5 MHz, THF-d8, -20 °C): δ -0.69 (s).
7
C{1H} NMR (100.6 MHz, THF-d8, -20 °C): δ 195.3 (Ph-ipso-C), 144.4 (Ph-o-CH), 124.6 (Ph-m-CH), 117.5
13
(Ph-p-CH), 87.2 (CDT-CH), 82.4 (CDT-CH), 69.2 (12-crown-4-CH2), 40.5 (CDT-CH2), 38.7 (CDT-CH2).
Elemental Analysis: Calculated for C34H55LiNiO8: C, 62.12; H, 8.43. Found: C, 62.16; H, 8.43.
Synthesis of Li2(TMEDA)2Ph2Ni(η2-CDT) (2)
Ni(ttt-CDT) (44.2 mg, 0.2 mmol) was dissolved in Et2O (0.5 mL) and cooled to -30 °C. PhLi (34.2 mg, 0.4
mmol) was slowly added as a chilled solution in Et2O (0.5 mL) followed by TMEDA (75 µL, 0.5 mmol). The
orange/red solution was warmed to room temperature and stirred for 15 minutes, then filtered and stored
at -30 °C for crystallisation. After 4 hours, the orange/brown solids were decanted from the supernatant,
washed with cold pentane (2 × 0.5 mL) and dried under argon. Yield – 20 mg (16%).
H NMR (300.1 MHz, THF-d8): δ 7.91 (d, J = 6.7 Hz, 4H, Ph-o-CH), 6.71 (t, J = 7.1 Hz, 4H, Ph-m-CH),
1
6.49 (t, J = 6.9 Hz, 2H, Ph-p-CH), 5.35–5.19 (m, 2H, CDT-CH), 5.12–4.96 (m, 2H, CDT-CH), 2.30 (s, 8H,
TMEDA-CH2), 2.14 (s, 24H, TMEDA-CH3), 2.14–1.98 (m, 4H + 2H, CDT-CH2), 1.96–1.74 (m, 4H, CDTCH2), 1.06–0.90 (m, 2H, CDT-CH2), 0.16 (d, J = 6.6 Hz, 2H, CDT-CH-coordinated).
Li NMR (116.6 MHz, THF-d8): δ 0.38 (s).
7
C{1H} NMR (75.5 MHz, THF-d8): δ 191.9 (Ph-ipso-C), 142.5 (Ph-o-CH), 137.0 (CDT-CH), 127.3 (CDT-
13
CH), 125.9 (Ph-m-CH), 119.2 (Ph-p-CH), 59.1 (TMEDA-CH2), 46.8 (CDT-CH-coordinated), 46.4 (TMEDACH3), 37.3 (CDT-CH2), 36.8 (CDT-CH2), 32.6 (CDT-CH2).
Elemental Analysis: Calculated for C36H60Li2N4Ni: C, 69.58; H, 9.73; N, 9.02. Found: C, 68.97; H, 9.91;
N, 8.87.
Synthesis of Li4(TMEDA)2(Et2O)2Ph4Ni2(µ;η2;η2-C6H4) (3)
Ni(ttt-CDT) (44.2 mg, 0.2 mmol) was dissolved in Et2O (1 mL) and PhLi (43 mg, 0.5 mmol) was added
followed by TMEDA (300 µL, 2.0 mmol). The reaction was stirred at room temperature for 3 days giving a
deep red solution which was filtered and stored at -30 °C for crystallisation via pentane vapour diffusion.
After 1 week, the supernatant was decanted from the dark red crystals, which were washed with cold
pentane (2 × 0.5 mL) and dried under argon. Yield – 30 mg (33%).
H NMR (300.1 MHz, THF-d8): δ 8.12 (d, J = 6.0 Hz, 8H, Ph-o-CH), 6.71–6.63 (m, 10H, Ph-m-CH + H3),
1
6.48 (tt, J = 7.2, 1.6 Hz, 4H, Ph-p-CH), 5.77 (dd, J = 5.5, 2.5 Hz, 2H, H2), 3.39 (q, Et2O-CH2), 2.31 (s, 8H,
TMEDA-CH2), 2.15 (s, 24H, TMEDA-CH3), 1.12 (t, Et2O-CH3).
Li NMR (116.1 MHz, THF-d8): δ 0.50 (vbr), -0.24 (vbr).
7
C{1H} NMR (75.5 MHz, THF-d8): δ 185.6 (Ph-ipso-C), 144.1 (Ph-o-CH), 126.0 (Ph-m-C), 125.2 (C3),
13
120.6 (Ph-p-CH), 115.9 (C2), 71.8 (br, C1), 66.5 (Et2O-CH2), 59.1 (TMEDA-CH2), 46.4 (TMEDA-CH3), 15.8
(Et2O-CH3).
Elemental Analysis: Calculated for C50H76Li4N4Ni2O2: C, 65.97; H, 8.42; N, 6.15. Found: C, 65.65; H,
8.26; N, 6.04.
Synthesis of Li2(THF)4Ph2Ni(η2-anthracene) (4Li)
Ni(ttt-CDT) (22.1 mg, 0.1 mmol) was dissolved in Et2O (1 mL) and cooled to -30 °C. PhLi (17.1 mg, 0.2
mmol) was added and the solution was warmed to room temperature, stirred for 2-3 minutes, then recooled
to -30 °C. Anthracene (17.8 mg, 0.1 mmol) was added followed by THF (0.1 mL) and the dark red reaction
mixture was stirred at -30 °C for 5 minutes, then filtered and stored at -30 °C for crystallisation via pentane
vapour diffusion. After 72 hours, the supernatant was decanted from the dark red/black crystals, which
were washed with cold pentane (2 × 0.5 mL) and dried under argon. Yield – 36 mg (52%).
H NMR (300.1 MHz, THF-d8): δ 8.00 (d, J = 6.7 Hz, 2H, Ph-o-CH), 7.44 (d, J = 6.7 Hz, 2H, Ph-o-CH),
1
7.00 (m, 2H, H6), 6.69–6.59 (m, 4H, Ph-m-CH + H7), 6.59–6.51 (m, 2H, Ph-m-CH), 6.49–6.37 (m, 4H, Php-CH + H4), 4.44 (br, 4H, H1/2), 3.62 (THF), 1.78 (THF).
Li NMR (116.6 MHz, THF-d8): δ 0.26 (br).
7
C{1H} NMR (75.5 MHz, THF-d8): δ 189.8 (ipso-C), 184.5 (ipso-C), 143.1 (C3), 142.1 (o-CH), 140.7 (o-
13
CH), 134.6 (C5), 125.1 (m-CH), 124.3 (m-CH), 124.1 (C6), 120.3 (C7), 119.4 (p-CH), 119.3 (p-CH), 113.5
(C4), 90.3 (C2), 73.8 (C1).
Elemental Analysis: Calculated for C42H52Li2NiO4: C, 72.75; H, 7.56. Found: C, 72.68; H, 7.73.
Synthesis of Na2(TMEDA)2Ph2Ni(η2-anthracene) (4Na)
Ni(ttt-CDT) (22.1 mg, 0.1 mmol) was dissolved in Et2O (1 mL) and cooled to -30 °C. PhLi (17.1 mg, 0.2
mmol) was added and the solution was warmed to room temperature, stirred for 2-3 minutes, then recooled
to -30 °C. Anthracene (17.8 mg, 0.1 mmol) was added followed by toluene (1 mL), NaOtBu (24 mg, 0.25
mmol) and TMEDA (90 µL, 0.6 mmol) and the dark green reaction mixture was stirred at -30 °C for 5
minutes, then filtered and stored at -30 °C for crystallisation via pentane vapour diffusion. After 72 hours,
the supernatant was decanted from the dark green/black crystals, which were washed with cold pentane
(2 × 0.5 mL) and dried under argon. Yield – 28 mg (42%).
H NMR (300.1 MHz, THF-d8): δ 7.60 (m, 4H, Ph-o-CH), (m, 4H, Ph-m-CH), 6.87 (dd, J = 3.3, 2.6 Hz, 2H,
1
H6), 6.70–6.62 (m, 4H, Ph-m-CH), 6.60–6.50 (m, 4H, Ph-p-CH + H7), 6.35 (s, 2H, H4), 4.58 (dd, J = 2.8,
2.3 Hz, 2H, H2), 4.42 (dd, J = 2.8, 2.3 Hz, 2H, H1), 2.30 (s, 8H, TMEDA-CH2), 2.15 (s, 24H, TMEDA-CH3).
C{1H} NMR (75.5 MHz, THF-d8): δ 182.3 (Ph-ipso-C), 175.4 (Ph-ipso-C), 143.78 (C3), 142.8 (Ph-o-CH),
13
142.2 (Ph-o-CH), 134.6 (C5), 126.3 (Ph-m-CH), 126.0 (Ph-m-CH), 123.9 (C6), 120.8 (C7), 119.9 (Ph-pCH), 109.7 (C4), 86.5 (C2), 72.2 (C1), 59.1 (TMEDA-CH2), 46.4 (TMEDA-CH3).
Elemental Analysis: Calculated for C38H52N4Na2Ni: C, 68.17; H, 7.83; N, 8.37. Found: C, 66.6; H, 7.67;
N, 7.66.
N.B. Crystalline samples were consistently low in carbon, hydrogen and nitrogen suggesting partial
TMEDA decoordination.
Synthesis of K2(PMDETA)2Ph2Ni(η2-anthracene) (4K)
Ni(ttt-CDT) (22.1 mg, 0.1 mmol) was dissolved in Et2O (1 mL) and cooled to -30 °C. PhLi (17.1 mg, 0.2
mmol) was added and the solution was warmed to room temperature, stirred for 2-3 minutes, then recooled
to -30 °C. Anthracene (17.8 mg, 0.1 mmol) was added followed by toluene (1 mL), KO tBu (28 mg, 0.25
mmol) and PMDETA (125 µL, 0.6 mmol) and the dark green reaction mixture was stirred at -30 °C for 5
minutes, then filtered and stored at -30 °C for crystallisation via pentane vapour diffusion. After 72 hours,
the supernatant was decanted from the dark green/black crystals, which were washed with cold pentane
(2 × 0.5 mL) and dried under argon. Yield – 22 mg (24%).
H NMR (300.1 MHz, THF-d8): δ 7.69 (m, 4H, Ph-o-CH), 6.72 (dd, J = 3.6, 2.1 Hz, 2H, H6), 6.69–6.60 (m,
1
4H, Ph-m-CH), 6.51–6.44 (m, 2H, Ph-p-CH), 6.48 (dd, J = 3.6, 2.1 Hz, 2H, H7), 6.17 (s, 2H, H4), 4.50 (m,
H2), 4.24 (m, 2H, H1), 2.41 (m, 8H, PMDETA-CH2), 2.31 (m, 8H, PMDETA-CH2), 2.19 (s, 6H, PMDETACH3), 2.15 (s, 24H, PMDETA-CH3).
C{1H} NMR (75.5 MHz, THF-d8): δ 144.7 (C3), 142.5 (Ph-o-CH), 141.9 (Ph-o-CH), 134.8 (C5), 126.0
13
(Ph-m-CH), 125.5 (Ph-m-CH), 123.0 (C6), 120.3 (C7), 119.6 (Ph-p-CH), 119.0 (Ph-p-CH), 106.8 (C4), 87.1
(C2), 73.1 (C1), 59.0 (PMDETA-CH2), 57.5 (PMDETA-CH2), 46.5 (PMDETA-CH3), 43.5 (PMDETA-CH3).
N.B. Due to poor solubility and limited stability at room temperature, signals for the Ph-ipso-carbons could
not be observed in the 13C{1H} or 1H-13C HMBC spectra.
Elemental Analysis: Calculated for C44H66K2N6Ni: C, 64.77; H, 8.15; N, 10.30. Found: C, 64.08; H, 8.01;
N, 9.78.
N.B. Crystalline samples were consistently low in carbon, hydrogen and nitrogen suggesting partial
PMDETA decoordination.
Synthesis of Li2(THF)4Ph2Ni(η2-phenanthrene) (5Li)
Ni(ttt-CDT) (22.1 mg, 0.1 mmol) was dissolved in Et2O (1 mL) and cooled to -30 °C. PhLi (17.1 mg, 0.2
mmol) was added and the solution was warmed to room temperature, stirred for 2-3 minutes, then recooled
to -30 °C. Phenanthrene (17.8 mg, 0.1 mmol) was added followed by THF (0.1 mL) and the dark red
reaction mixture was stirred at -30 °C for 5 minutes, then filtered and stored at -30 °C for crystallisation via
pentane vapour diffusion. After 72 hours, the supernatant was decanted from the dark red/brown crystals,
which were washed with cold pentane (2 × 0.5 mL) and dried under argon. Yield – 38 mg (55%).
H NMR (300.1 MHz, THF-d8): δ 7.50 (d, J = 6.5 Hz, 4H, Ph-o-CH), 7.38 (d, J = 7.6 Hz, 2H, H6), 6.64–
1
6.56 (m, 6H, Ph-m-CH + H5), 6.48–6.39 (m, 4H, Ph-p-CH + H4), 6.27 (d, J = 7.0 Hz, 2H, H3), 3.62 (THF),
2.78 (s, 2H, H1), 1.78 (THF).
Li NMR (116.6 MHz, THF-d8): δ -0.27 (s).
7
C{1H} NMR (75.5 MHz, THF-d8): δ 189.7 (Ph-ipso-C), 145.7 (C7), 142.0 (Ph-o-CH), 129.6 (C2), 126.8
13
(C3), 126.0 (C5), 124.6 (Ph-m-CH), 121.0 (C6), 119.2 (Ph-p-CH), 116.3 (C4), 39.0 (C1).
Elemental Analysis: Calculated for C42H52Li2NiO4: C, 72.75; H, 7.56. Found: C, 71.69; H, 7.57.
Spectroscopically pure and crystalline samples were consistently low in carbon.
Synthesis of [Na2(THF)3Ph2Ni(η2-phenanthrene)]2 (5Na)
Ni(ttt-CDT) (22.1 mg, 0.1 mmol) was dissolved in Et2O (1 mL) and cooled to -30 °C. PhLi (17.1 mg, 0.2
mmol) was added and the solution was warmed to room temperature, stirred for 2-3 minutes, then recooled
to -30 °C. Phenanthrene (17.8 mg, 0.1 mmol) was added followed by THF (0.1 mL) and NaOtBu (24 mg,
0.25 mmol) and the dark red reaction mixture was stirred at -30 °C for 5 minutes, then filtered and stored
at -30 °C for crystallisation via pentane vapour diffusion. After 48 hours, the supernatant was decanted
from the dark red/black crystals, which were washed with cold pentane (2 × 0.5 mL) and dried under argon.
Yield – 41 mg (63%).
H NMR (300.1 MHz, THF-d8): δ 7.53 (d, J = 6.7 Hz, 4H, Ph-o-CH), 7.37 (d, J = 7.8 Hz, 2H, H6), 6.69-6.56
1
(m, 8H, Ph-m-CH + H3 + H5), 6.53-6.41 (m, 4H, Ph-p-CH + H5), 3.62 (THF), 3.05 (s, 2H, H1), 1.78 (THF).
C{1H} NMR (75.5 MHz, THF-d8): δ 187.8 (Ph-ipso-C), 146.5 (C7), 142.4 (Ph-o-CH), 129.0 (C2), 126.9
13
(C5), 125.5 (Ph-m-CH), 125.1 (C3), 121.5 (C6), 119.5 (Ph-p-CH), 116.7 (C4), 38.9 (C1).
Elemental Analysis: Calculated for C38H44Na2NiO3: C, 69.85; H, 6.79. Found: C, 69.30; H, 6.82.
Synthesis of [K2(THF)1Ph2Ni(η2-phenanthrene)]∞ (5K)
Ni(ttt-CDT) (22.1 mg, 0.1 mmol) was dissolved in Et2O (1 mL) and cooled to -30 °C. PhLi (17.1 mg, 0.2
mmol) was added and the solution was warmed to room temperature, stirred for 2-3 minutes, then recooled
to -30 °C. Phenanthrene (17.8 mg, 0.1 mmol) was added followed by THF (0.1 mL) and KO tBu (28 mg,
0.25 mmol) and the dark red reaction mixture was stirred at -30 °C for 5 minutes, then filtered and stored
at -30 °C for crystallisation via pentane vapour diffusion. After 72 hours, the supernatant was decanted
from the dark purple/black crystals, which were washed with cold pentane (2 × 0.5 mL) and dried under
argon. Yield – 23 mg (43%).
H NMR (300.1 MHz, THF-d8): δ 7.64 (dd, J = 7.5, 1.4 Hz, 4H, Ph-ortho-CH), 7.27 (d, J = 7.2 Hz, 2H, H6),
1
6.62 (m, 6H, Ph-meta-CH + H3), 6.49 (td, J = 7.9, 1.2 Hz, 2H, H5), 6.43 (tt, J = 7.2, 1.5 Hz, 2H, Ph-paraCH), 6.34 (td, J = 6.8, 1.4 Hz, 2H, H4), 3.62 (THF), 3.09 (s, 2H, H1), 1.78 (THF).
C{1H} NMR (75.5 MHz, THF-d8): δ 193.7 (Ph-ipso-C), 147.6 (C7), 142.7 (Ph-ortho-CH), 128.2 (C2), 127.1
13
(C5), 125.4 (Ph-meta-CH), 124.2 (C3), 121.5 (C6), 118.5 (Ph-para-CH), 115.8 (C4), 40.5 (C1).
Elemental Analysis: Calculated for C30H28K2NiO: C, 66.55; H, 5.21. Found: C, 66.25; H, 5.21.
Synthesis of [Li(THF)2Ph2Ni(η3-perylene)][Li(THF)4] (6Li)
Ni(ttt-CDT) (22.1 mg, 0.1 mmol) was dissolved in Et2O (1 mL) and cooled to -30 °C. PhLi (17.1 mg, 0.2
mmol) was added and the solution was warmed to room temperature, stirred for 2-3 minutes, then recooled
to -30 °C. Perylene (25.2 mg, 0.1 mmol) was added followed by THF (0.5 mL) and the dark purple reaction
mixture was stirred at -30 °C for 5 minutes, then filtered and stored at -30 °C for crystallisation via pentane
vapour diffusion. After 72 hours, the supernatant was decanted from the dark blue/purple crystals, which
were washed with cold pentane (2 × 0.5 mL) and dried under argon. Yield – 65 mg (71%).
N.B. Isolated samples were contaminated with small bronze crystals identified as the perylene radical
anion by EPR spectroscopy (see Figure S5) and could therefore not be isolated in pure form for suitable
elemental analysis.
H NMR (300.1 MHz, THF-d8): δ 7.89 (d, J = 6.9 Hz, 2H), 7.54 (d, J = 6.8 Hz, 2H), 6.80–6.65 (m, 6H),
1
6.59–6.47 (m, 4H), 6.23 (t, J = 7.4 Hz, 2H), 6.08 (d, J = 7.2 Hz, 2H), 5.84 (br, 2H), 5.65 (br, 2H), 4.60 (vbr,
2H), 3.62 (THF), 1.78 (THF).
Li NMR (116.6 MHz, THF-d8): δ -0.68 (s).
7
C{1H} NMR (75.5 MHz, THF-d8): δ 178.5, 176.2, 143.0, 139.7, 129.1, 125.3, 125.2, 121.2, 114.6. Signals
13
for the coordinated perylene could not be observed in the 13C{1H}, 1H-13C HSQC or 1H-13C HMBC spectra.
Synthesis of [Li(THF)2Ph2Ni(η2-coronene)][Li(THF)4] (7Li)
Ni(ttt-CDT) (22.1 mg, 0.1 mmol) was dissolved in Et2O (1 mL) and cooled to -30 °C. PhLi (17.1 mg, 0.2
mmol) was added and the solution was warmed to room temperature, stirred for 2-3 minutes, then recooled
to -30 °C. Coronene (30.0 mg, 0.1 mmol) was added followed by THF (1 mL) and the dark reaction mixture
was stirred at -30 °C for 5 minutes, then filtered and stored at -30 °C for crystallisation via pentane vapour
diffusion. After 48 hours, the supernatant was decanted from the dark black/green crystals, which were
washed with cold pentane (2 × 0.5 mL) and dried under argon. Yield – 24 mg (24%).
H NMR (400.1 MHz, THF-d8, -20 °C): δ 7.45 (s, 2H), 7.39 (d, J = 6.5 Hz, 4H, Ph-o-CH), 7.10 (s, 4H), 6.98
1
(d, J = 7.9 Hz, 2H), 6.59 (t, J = 7.0 Hz, 4H, Ph-m-CH), 6.41–6.32 (m, 2H + 2H, Ph-p-CH), 3.62 (THF), 3.30
(s, 2H), 1.78 (THF).
Li NMR (155.5 MHz, THF-d8, -40 °C): δ 0.52 (br), 0.00 (br).
7
C{1H} NMR (100.6 MHz, THF-d8, -20 °C): δ 189.6 (Ph-ipso-C), 142.0, 140.6 (Ph-o-CH), 130.6, 128.7,
13
128.6, 128.4, 125.1, 124.5, 124.4, 124.2 (Ph-m-CH), 123.3, 119.7, 119.0 (Ph-p-CH), 42.3.
Elemental Analysis: Calculated for C60H70Li2NiO6: C, 75.09; H, 7.35. Found: C, 74.91; H, 7.35.
Synthesis of K2(DME)4Ph2Ni(η2-coronene) (7K)
Ni(ttt-CDT) (11.0 mg, 0.05 mmol) was dissolved in Et2O (1 mL) and cooled to -30 °C. PhLi (8.6 mg, 0.1
mmol) was added and the solution was warmed to room temperature, stirred for 2-3 minutes, then recooled
to -30 °C. Coronene (15.0 mg, 0.05 mmol) was added slowly as a solution/suspension in DME (1 mL),
followed by KOtBu (14 mg, 0.125 mmol) and the black reaction mixture was stirred at -30 °C for 5 minutes,
then filtered and stored at -30 °C for crystallisation via pentane vapour diffusion. After 72 hours, the
supernatant was decanted from the dark black crystals, which were washed with cold pentane (2 × 0.5
mL) and dried under argon. Yield – 21 mg (44%).
N.B. Isolated samples were found to be contaminated with the coronene radical anion by EPR
spectroscopy (see Figure S8) and could therefore not be isolated in pure form for suitable elemental
analysis.
H NMR (300.1 MHz, THF-d8): δ 7.62 (d, J = 6.7 Hz, 4H, Ph-o-CH), 7.18 (vbr, coronene), 6.62 (t, J = 6.9
1
Hz, 4H, Ph-m-CH), 6.41 (t, J = 6.9 Hz, 2H, Ph-p-CH), 3.53 (DME-CH2), 3.35 (DME-CH3).
N.B. Due to poor solubility of 7K, low temperature measurements were not possible.
Synthesis of [Li2(THF)3Ph2Ni(η2-Ph2CO)]2 (8Li)
Ni(ttt-CDT) (22.1 mg, 0.1 mmol) was dissolved in Et2O (1 mL) and cooled to -30 °C. PhLi (17.1 mg, 0.2
mmol) was added and the solution was warmed to room temperature, stirred for 2-3 minutes, then recooled
to -30 °C. Benzophenone (18.2 mg, 0.1 mmol) was added followed by THF (0.1 mL) and the dark
purple/green reaction mixture was stirred at -30 °C for 5 minutes, then filtered and stored at -30 °C for
crystallisation via pentane vapour diffusion. After 72 hours, the supernatant was decanted from the dark
purple crystals, which were washed with cold pentane (2 × 0.5 mL) and dried under argon. Yield – 39 mg
(62%).
N.B. The 1H NMR spectrum of 8Li was very broad at room temperature and whilst cooling to -20 °C does
lead to improvement of resolution and sharpening of signals, the significant overlap means it is not possible
to confidently assign signals (see Spectra 33–35).
Elemental Analysis: Calculated for C37H44Li2NiO4: C, 71.07; H, 7.09. Found: C, 70.58; H, 7.14.
Synthesis of [K2(DME)3Ph2Ni(η2-Ph2CO)]2 (8K)
Ni(ttt-CDT) (22.1 mg, 0.1 mmol) was dissolved in Et2O (1 mL) and cooled to -30 °C. PhLi (17.1 mg, 0.2
mmol) was added and the solution was warmed to room temperature, stirred for 2-3 minutes, then recooled
to -30 °C. Benzophenone (18.2 mg, 0.1 mmol) was added followed by DME (0.5 mL) and KOtBu (28 mg,
0.25 mmol) and the black reaction mixture was stirred at -30 °C for 5 minutes, then filtered and stored at 30 °C for crystallisation via pentane vapour diffusion. After 72 hours, the supernatant was decanted from
the dark blue crystals, which were washed with cold pentane (2 × 0.5 mL) and dried under argon. Yield –
37 mg (50%).
H NMR (300.1 MHz, THF-d8): δ 7.99 (d, J = 5.9 Hz, 2H, Ph-o-CH), 7.40 (d, J = 7.0 Hz, 4H, Ph2CO-o-CH),
1
7.28 (d, J = 7.0 Hz, 2H, Ph-o-CH), 6.90 (t, J = 6.9 Hz, 4H, Ph2CO-m-CH), 6.77 (t, J = 6.3 Hz, 2H, Ph2COp-CH), 6.64 (d, J = 6.9 Hz, 2H, Ph-m-CH), 6.59 (d, J = 6.7 Hz, 1H, Ph-p-CH), 6.41 (t, J = 7.0 Hz, 2H, Phm-CH), 6.29 (t, J = 7.0 Hz, 1H, Ph-o-CH), 3.43 (DME-CH2), 3.27 (DME-CH3).
C{1H} NMR (75.5 MHz, THF-d8): δ 185.4 (Ph-ipso-C), 153.6 (Ph2CO-ipso-C), 143.1 (br, Ph-o-CH), 141.2
13
(Ph-o-CH), 127.9 (Ph2CO-m-CH), 125.9 (Ph2CO-p-CH), 124.8 (br, Ph2CO-o-CH), 124.5 (Ph-m-CH), 120.0
Ph-p-CH), 118.7 (Ph-m-CH), 117.7 (Ph-p-CH), 72.9 (DME-CH2), 59.1 (DME-CH3).
N.B. Signals for the carbonyl carbon not observed in the 13C{1H} or 1H-13C HMBC spectra.
Elemental Analysis: Calculated for C37H50K2NiO7: C, 59.76; H, 6.78. Found: C, 59.72; H, 6.60.
Synthesis of Li2(THF)5Ph2Ni(η2-PhCH=NPh) (9Li)
Ni(ttt-CDT) (22.1 mg, 0.1 mmol) was dissolved in Et2O (1 mL) and cooled to -30 °C. PhLi (17.1 mg, 0.2
mmol) was added and the solution was warmed to room temperature, stirred for 2-3 minutes, then recooled
to -30 °C. N-benzylideneaniline (18.1 mg, 0.1 mmol) was added followed by THF (0.1 mL) and the red
reaction mixture was stirred at -30 °C for 5 minutes, then filtered and stored at -30 °C for crystallisation via
pentane vapour diffusion. After 72 hours, the supernatant was decanted from the bright red crystals, which
were washed with cold pentane (2 × 0.5 mL) and dried under argon. Yield – 31 mg (50%).
H NMR (300.1 MHz, THF-d8): 8.00 (d, J = 6.4 Hz, 2H, H2/6), 7.87 (d, J = 6.4 Hz, 2H, H2/6), 6.92–6.83
1
(m, 2H + 2H, H3/7 + H15), 6.77–6.68 (m, 2H + 2H + 2H +1H, H3/7 + H11, H12, H4/8), 6.68–6.59 (m, 2H,
H16), 6.59–6.48 (m, 1H + 1H, H4/8 + H13), 6.38 (t, J = 7.1 Hz, 1H, H17), 3.81 (s, 1H, H9), 3.62 (THF),
1.77 (THF).
Li NMR (116.6 MHz, THF-d8): -0.12 (s).
7
C{1H} NMR (75.5 MHz, THF-d8): 181.8 (C1/5), 179.7 (C1/5), 161.0 (C14), 153.6 (C10), 143.7 (C2/6),
13
142.4 (C2/6), 128.6 (C15), 127.8 (C12), 126.0 (C3/7), 125.7 (C3/7), 124.8 (C11), 121.7 (C4/8), 120.9
(C16), 120.3 (C13), 119.8 (C4/8), 114.4 (C17), 67.6 (THF), 53.7 (C9), 25.5 (THF).
Elemental Analysis: Calculated for C45H61Li2NNiO5: C, 70.33; H, 8.00; N, 1.82. Found: C, 70.30; H, 8.07;
N, 1.74.
N.B. NMR spectroscopy and elemental analysis consistent with three molecules of coordinated THF.
Synthesis of [Li2(THF)3Ph2Ni(η2-Ph2CHCN)]2 (10Li)
Ni(ttt-CDT) (22.1 mg, 0.1 mmol) was dissolved in Et2O (1 mL) and cooled to -30 °C. PhLi (17.1 mg, 0.2
mmol) was added and the solution was warmed to room temperature, stirred for 2-3 minutes, then recooled
to -30 °C. Diphenylacetonitrile (19.3 mg, 0.1 mmol) was added slowly as a chilled solution in THF (1 mL)
and the amber reaction mixture was stirred at -30 °C for 5 minutes, then filtered and stored at -30 °C for
crystallisation via pentane vapour diffusion. After 48 hours, the supernatant was decanted from the bright
yellow crystals, which were washed with cold pentane (2 × 0.5 mL) and dried under argon. Yield – 27 mg
(42%).
H NMR (400.1 MHz, THF-d8, -20 °C): δ 8.10 (d, J = 6.9 Hz, 2H), 7.89 (d, J = 6.7 Hz, 2H), 7.52–7.35 (m,
1
4H), 7.05 (m, 4H), 6.98 (m, 2H), 6.90 (br, 2H), 6.72 (br, 3H), 6.60–6.47 (m, 2H), 5.29 (br, 1H), 3.62 (THF),
1.78 (THF).
Li NMR (155.5 MHz, THF-d8, -20 °C): δ 0.33 (br).
7
N.B. Due to poor solution-state stability and low solubility at low temperatures, suitable 13C{1H} NMR
spectral data could not be obtained.
Elemental Analysis: Calculated for C38H45Li2NNiO3: C, 71.72; H, 7.13; N, 2.20. Found: C, 71.01; H, 7.09;
N, 2.09.
Synthesis of Li(THF)3(PPh3)2(CO)3Ni2(µ-PPh2) (11Li)
(Ph3P)2Ni(CO)2 (25.5 mg, 0.04 mmol) was dissolved in THF-d8 (0.5 mL) and PhLi (6.8 mg, 0.08 mmol) was
added at room temperature resulting in a colour change from colourless to deep red. New signals were
observed in the 31P NMR spectrum at δ 45.5 and 28.7 ppm which grew in intensity over the course of 2
days as the signal for the starting material (δ 32.6) disappeared. Additional signals at δ 31.5 (unidentified
species) and -5.5 (Ph3P) were also observed, alongside numerous minor signals. The solution was
decanted into a vial and stored at -30 °C for crystallisation via pentane vapour diffusion. After 72 hours,
red crystals of 11Li suitable for X-ray diffraction were obtained. The supernatant was decanted and the
solids were washed with cold pentane (0.5 mL) and dried under argon. Yield – 6 mg (26%).
H NMR (300.1 MHz, THF-d8): δ 7.34 (br, 12H), 7.20–7.02 (m, 22H), 6.48 (m, 6H).
1
Li NMR (116.6 MHz, THF-d8): δ -0.62 (br).
7
P NMR (121.5 MHz, THF-d8): δ 45.7 (s, 1P), 28.7 (s, 2P).
31
Variable Temperature NMR Spectroscopy
[Li(THF)2Ph2Ni(η2-coronene)][Li(THF)4] (7Li)
15 mg of [Li(THF)2Ph2Ni(η2-coronene)][Li(THF)4] (7Li) was dissolved in THF-d8 (0.5 mL) and analysed by
1
H and 7Li NMR spectroscopy at +20 °C, +10 °C, 0 °C, -10 °C, -20 °C, -30 °C and -40 °C (Figures S1–2).
Figure S1: Stacked 1H NMR spectra at variable temperatures for [Li(THF)2Ph2Ni(η2-coronene)][Li(THF)4]
(7Li).
Figure S2: Stacked 7Li NMR spectra at variable temperatures for [Li(THF)2Ph2Ni(η2-coronene)][Li(THF)4]
(7Li).
DOSY NMR Spectroscopy
Estimated molecular weights (MW) were calculated from the diffusion coefficients established from the 1H
DOSY NMR spectrum using Stalke’s external calibration curve (ECC) method5–7 and using
tetramethylsilane as an internal standard. Samples were prepared by dissolving 0.0075 mmol each of
complex and internal standard in 500 µL of THF-d8 to give a concentration of 15 mM.
[Na2(THF)3Ph2Ni(η2-phenanthrene)]2 (5Na)
Predicted molecular weight for Na2(THF)4Ph2Ni(η2-phenanthrene) = 725.55 g mol-1. Estimated molecular
weights determined from diffusion coefficients = 683 g mol-1 (Merge), 6% difference; 626 g mol-1 (DSE),
16% difference (Figure S3).
Figure S3: 1H DOSY NMR spectrum of [Na2(THF)3Ph2Ni(η2-phenanthrene)]2 (5Na) in THF-d8.
[K2(THF)1Ph2Ni(η2-phenanthrene)]∞ (5K)
Predicted molecular weight for K2(THF)4Ph2Ni(η2-phenanthrene) = 757.76 g mol-1. Estimated molecular
weights determined from diffusion coefficients = 713 g mol-1 (Merge), 6% difference; 652 g mol-1 (DSE),
16% difference (Figure S4).
Figure S4: 1H DOSY NMR spectrum of [K2(THF)1Ph2Ni(η2-phenanthrene)]∞ (5K) in THF-d8.
EPR Spectroscopy
Samples for EPR spectroscopy were prepared by dissolving approximately 1 mg of compound in 1 mL of
THF and transferring 50 µL to a 1.5 mm inset capillary that was placed within a quartz EPR tube and
sealed.
Figure S5: EPR spectrum of crystalline [Li(THF)2Ph2Ni(η3-perylene)][Li(THF)4] (6Li) contaminated with
the perylene radical anion.
Figure S6: EPR spectrum of the solids isolated during the attempted synthesis of
Na2(solv)nPh2Ni(perylene).
Figure S7: EPR spectrum of isolated [perylene][K(DME)4] during the attempted synthesis of
K2(solv)nPh2Ni(perylene).
Figure S8: EPR spectrum of crystalline K2(DME)4Ph2Ni(η2-coronene) (7K) contaminated with the
coronene radical anion.
X-Ray Crystallography
The crystal structures of all novel compounds have been deposited into the Cambridge Crystallographic
Data Centre (CCDC) and have been assigned the following numbers: 2326086–2326102. Selected
crystallographic and refinement parameters are presented below (Tables S1–5). In all cases, crystals
immersed in an inert parabar oil were mounted at low temperatures and transferred into the nitrogen
stream (100 or 173 K). Perfluorinated oils must be avoided for the alkali-metal nickelates.
All measurements were made on a RIGAKU Synergy S area-detector diffractometer using mirror optics
monochromated Cu Kα radiation (λ = 1.54184 Å) or on a RIGAKU XtaLAB Synergy R, HyPix-Arc 100 areadetector diffractometer using mirror optics monochromated Mo Kα radiation (λ = 0.71073 Å). Data
reduction was performed using the CrysAlisPro program.8 The intensities were corrected for Lorentz and
polarization effects, and an absorption correction based on the Gaussian method using SCALE3
ABSPACK in CrysAlisPro was applied. The structure was solved by direct methods or intrinsic phasing
using SHELXT,9 which revealed the positions of all non-hydrogen atoms of the compounds. All nonhydrogen atoms were refined anisotropically. H-atoms were assigned in geometrically calculated positions
and refined using a riding model where each H-atom was assigned a fixed isotropic displacement
parameter with a value equal to 1.2Ueq of its parent atom (1.5Ueq for methyl groups). Refinement of the
structure was carried out on F2 using full-matrix least-squares procedures, which minimized the function
Σw(Fo2 – Fc2)2. The weighting scheme was based on counting statistics and included a factor to downweight
the intense reflections. All calculations were performed using the SHELXL-2014/7 program10 in OLEX2.11
For [(ttt-CDT)NiPh][Li(12-crown-4)2] (1), a disorder model was used for parts of the ttt-CDT ligand and
12-crown-4 where the occupancies of each disorder component was refined through the use of a free
variable. The sum of equivalent components was constrained to 1, i.e. 100%.
For Li4(TMEDA)2(Et2O)2Ph4Ni2(µ;η2;η2-C6H4) (3), a disorder model was used for parts of the coordinated
Et2O and TMEDA where the occupancies of each disorder component was refined through the use of a
free variable. The sum of equivalent components was constrained to 1, i.e. 100%.
For Li2(THF)4Ph2Ni(η2-anthracene) (4Li), a disorder model was used for the parts of the coordinated THF
where the occupancies of each disorder component were refined with the use of a free variable. The
sum of equivalent components was constraint to 1, i.e. 100%.
For Na2(TMEDA)2Ph2Ni(η2-anthracene) (4Na), a disorder model was used for the parts of the coordinated
TMEDA where the occupancies of each disorder component was refined through the use of a free variable.
The sum of equivalent components was constrained to 1, i.e. 100%.
For K2(PMDETA)2Ph2Ni(η2-anthracene) (4K), a disorder model was used for several parts of the structure
where the occupancies of each disorder component was refined through the use of a free variable. The
sum of equivalent components was constrained to 1, i.e. 100%.
For Li2(THF)4Ph2Ni(η2-phenanthrene) (5Li), a disorder model was used for parts of the coordinated THF
where the occupancies of each disorder component was refined through the use of a free variable. The
sum of equivalent components was constrained to 1, i.e. 100%.
For [Na2(THF)3Ph2Ni(η2-phenanthrene)]2 (5Na), a disorder model was used for parts of coordinated THF
where the occupancies of each disorder component was refined through the use of a free variable. The
sum of equivalent components was constrained to 1, i.e. 100%. Areas containing disordered solvents were
found where a satisfactory solvent model could not be achieved, therefore, a solvent mask was used to
include the contribution of electron density found in void areas into the calculated structure factor.
For [K2(THF)1Ph2Ni(η2-phenanthrene)]∞ (5K), twinning could be detected where the second and third twin
components corresponded to a rotation of -179.9272 degrees around [-0.00 -0.00 1.00] (reciprocal space),
or [0.11 0.00 0.99] (direct space) for twin component 2 and -162.9797 degrees around [-0.11 -0.01 0.99]
(reciprocal space), or [-0.20 -0.05 0.98] (direct space) for twin component 3. The refinement was performed
against the reflection file containing detwinned data of all 3 components on a hkl 5 format. The final refined
volume fractional contribution of twins 2 and 3 were 0.4870(9) and 0.02401(17) respectively.
For [Li(THF)2Ph2Ni(η3-perylene)][Li(THF)4] (6Li), a disorder model was used for coordinated THF
molecules where the occupancies of each disorder component was refined through the use of a free
variable. The sum of equivalent components was constrained to 1, i.e. 100%.
For [Li(THF)2Ph2Ni(η2-coronene)][Li(THF)4] (7Li), a disorder model was used for coordinated THF
molecules where the occupancies of each disorder component was refined through the use of a free
variable. The sum of equivalent components was constrained to 1, i.e. 100%.
For [Li2(THF)3Ph2Ni(η2-Ph2CO)]2 (8Li), a disorder model was used for parts of the coordinated THF where
the occupancies of each disorder component was refined through the use of a free variable. The sum of
equivalent components was constrained to 1, i.e. 100%. Areas containing disordered solvents were found
where a satisfactory solvent model could not be achieved, therefore, a solvent mask was used to include
the contribution of electron density found in void areas into the calculated structure factor.
For [K2(DME)3Ph2Ni(η2-Ph2CO)]2 (8K), A disorder model was used for parts of the coordinated DME where
the occupancies of each disorder component was refined through the use of a free variable. The sum of
equivalent components was constrained to 1, i.e. 100%. Areas containing disordered solvents were found
where a satisfactory solvent model could not be achieved, therefore, a solvent mask was used to include
the contribution of electron density found in void areas into the calculated structure factor.
For [Li2(THF)3Ph2Ni(η2-Ph2CHCN)]2 (10Li), a disorder model was used for parts of the coordinated THF
where the occupancies of each disorder component was refined through the use of a free variable. The
sum of equivalent components was constrained to 1, i.e. 100%. Areas containing disordered solvents were
found where a satisfactory solvent model could not be achieved, therefore, a solvent mask was used to
include the contribution of electron density found in void areas into the calculated structure factor.
For Li(THF)3(PPh3)2(CO)3Ni2(µ-PPh2) (11Li), a disorder model was used for parts of the coordinated THF
where the occupancies of each disorder component was refined through the use of a free variable. The
sum of equivalent components was constrained to 1, i.e. 100%. Areas containing disordered solvents were
found where a satisfactory solvent model could not be achieved, therefore, a solvent mask was used to
include the contribution of electron density found in void areas into the calculated structure factor.
Identification code
CCDC Number
Empirical formula
Formula weight
Temperature/K
Crystal system
Space group
a/Å
b/Å
c/Å
α/°
β/°
γ/°
Volume/Å3
Z
1
2326086
C34H55LiNiO8
657.43
100.01(10)
monoclinic
P21/n
15.15520(10)
10.28020(10)
21.0871(2)
90
93.3440(10)
90
3279.74(5)
4
3
2326087
C50H76Li4N4Ni2O2
910.32
173.00(10)
monoclinic
P21/n
10.94240(10)
20.8208(2)
22.7000(2)
90
95.7330(10)
90
5145.86(8)
4
4Li
2326088
C42H52Li2NiO4
693.42
173.00(10)
monoclinic
C2/c
23.83845(18)
10.06099(9)
31.2245(3)
90
92.8991(8)
90
7479.25(11)
8
4Na
2326089
C38H52N4Na2Ni
669.52
100.00(10)
monoclinic
P21/n
10.5871(2)
22.0003(3)
16.2275(2)
90
94.8440(10)
90
3766.20(10)
4
ρcalcg/cm3
1.331
1.175
1.232
1.181
μ/mm-1
F(000)
0.641
1416
0.173 × 0.107 ×
0.051
Mo Kα (λ = 0.71073)
0.771
1952
Mo Kα (λ = 0.71073)
1.048
2960
0.291 × 0.062 ×
0.041
Cu Kα (λ = 1.54184)
0.568
1432
0.266 × 0.093 ×
0.069
Mo Kα (λ = 0.71073)
4.41 to 60.162
4.104 to 60.068
5.668 to 148.956
4.282 to 61.016
Index ranges
-21 ≤ h ≤ 21, -14 ≤ k
≤ 14, -29 ≤ l ≤ 29
-15 ≤ h ≤ 15, -29 ≤ k
≤ 29, -31 ≤ l ≤ 31
-29 ≤ h ≤ 29, -12 ≤ k
≤ 12, -39 ≤ l ≤ 39
-15 ≤ h ≤ 15, -31 ≤ k
≤ 31, -23 ≤ l ≤ 23
Reflections
collected
191061
154783
75114
114953
Independent
reflections
9636 [Rint = 0.0343,
Rsigma = 0.0129]
15039 [Rint =
0.0334, Rsigma =
0.0203]
7639 [Rint = 0.0328,
Rsigma = 0.0179]
11482 [Rint =
0.0436, Rsigma =
0.0275]
9636/279/561
15039/245/717
7639/172/548
11482/100/486
Crystal size/mm3
Radiation
2Θ range for data
collection/°
0.16 × 0.123 × 0.05
Data/restraints/para
meters
Goodness-of-fit on
F2
Final R indexes
[I>=2σ (I)]
1.07
1.027
1.064
1.023
R1 = 0.0319, wR2 =
0.0778
R1 = 0.0307, wR2 =
0.0764
R1 = 0.0412, wR2 =
0.1189
R1 = 0.0429, wR2 =
0.0962
Final R indexes [all
data]
R1 = 0.0360, wR2 =
0.0794
R1 = 0.0419, wR2 =
0.0809
R1 = 0.0498, wR2 =
0.1260
R1 = 0.0672, wR2 =
0.1051
Largest diff.
peak/hole / e Å-3
0.46/-0.37
0.30/-0.24
0.45/-0.33
0.44/-0.31
Table S1: Crystal data and structure refinement details for compounds 1, 3, 4Li and 4Na.
Identification code
CCDC Number
4K
2326090
5Li
2326091
5Na
2326092
5K
2326093
Empirical formula
C44H66K2N6Ni
C42H52Li2NiO4
C76H88Na4Ni2O6
C30H28K2NiO
Formula weight
815.93
693.42
1306.84
541.43
Temperature/K
100.00(10)
173.00(10)
100.01(10)
173.01(10)
Crystal system
monoclinic
monoclinic
triclinic
monoclinic
Space group
P21/n
P21/n
P-1
P21/c
a/Å
19.97570(10)
16.7487(2)
12.22970(10)
12.46834(19)
b/Å
11.46590(10)
12.4289(2)
13.7829(2)
9.88563(16)
c/Å
21.46230(10)
18.2015(3)
21.3400(2)
20.5241(3)
α/°
90
90
106.7570(10)
90
β/°
112.3960(10)
101.5340(10)
99.6030(10)
93.8253(14)
γ/°
90
90
92.9580(10)
90
Volume/Å3
4544.93(6)
3712.45(10)
3377.08(7)
2524.11(7)
Z
4
4
2
4
ρcalcg/cm3
1.192
1.241
1.285
1.425
μ/mm-1
2.517
0.562
0.635
1.12
F(000)
1752
0.215 × 0.172 ×
0.097
Cu Kα (λ = 1.54184)
1480
0.176 × 0.134 ×
0.071
Mo Kα (λ = 0.71073)
1384
Mo Kα (λ = 0.71073)
1128
0.178 × 0.144 ×
0.110
Mo Kα (λ = 0.71073)
5.146 to 149.002
4.11 to 60.06
4.19 to 61.016
4.576 to 61.044
Index ranges
-24 ≤ h ≤ 24, -14 ≤ k
≤ 13, -26 ≤ l ≤ 26
-23 ≤ h ≤ 23, -17 ≤ k
≤ 17, -25 ≤ l ≤ 25
-17 ≤ h ≤ 17, -19 ≤ k
≤ 19, -30 ≤ l ≤ 30
-17 ≤ h ≤ 17, -14 ≤ k
≤ 14, -29 ≤ l ≤ 29
Reflections
collected
102150
108687
204216
23178
Independent
reflections
9294 [Rint = 0.0240,
Rsigma = 0.0125]
10860 [Rint =
0.0355, Rsigma =
0.0199]
20582 [Rint =
0.0484, Rsigma =
0.0307]
23178 [Rint = ?,
Rsigma = 0.0390]
9294/1134/735
10860/136/495
20582/202/893
23178/0/309
Crystal size/mm3
Radiation
2Θ range for data
collection/°
0.254 × 0.16 × 0.08
Data/restraints/para
meters
Goodness-of-fit on
F2
Final R indexes
[I>=2σ (I)]
1.086
1.029
1.048
1.163
R1 = 0.0557, wR2 =
0.1471
R1 = 0.0377, wR2 =
0.0971
R1 = 0.0610, wR2 =
0.1613
R1 = 0.0398, wR2 =
0.1211
Final R indexes [all
data]
R1 = 0.0583, wR2 =
0.1494
R1 = 0.0463, wR2 =
0.1012
R1 = 0.0884, wR2 =
0.1769
R1 = 0.0631, wR2 =
0.1279
Largest diff.
peak/hole / e Å-3
0.65/-0.63
0.45/-0.33
1.34/-0.61
1.21/-1.42
Table S2: Crystal data and structure refinement details for compounds 4K, 5Li, 5Na and 5K.
Identification code
CCDC Number
Empirical formula
Formula weight
Temperature/K
Crystal system
Space group
a/Å
b/Å
c/Å
α/°
β/°
γ/°
Volume/Å3
Z
6Li
2326094
C56H69Li2NiO6
910.7
173.00(10)
monoclinic
P21/c
17.8080(4)
13.0662(2)
22.5123(4)
90
111.093(2)
90
4887.25(17)
4
[perylene][K(DME)4]
2326095
C36H52KO8
651.87
100.01(10)
monoclinic
C2/c
23.11620(10)
13.75360(10)
11.45110(10)
90
96.5740(10)
90
3616.72(4)
4
7Li
2326096
C60H70Li2NiO6
959.75
173.01(10)
orthorhombic
Pbca
13.7527(2)
21.6279(4)
34.0256(5)
90
90
90
10120.6(3)
8
7K
2326097
C52H62K2NiO8
951.92
173.00(10)
orthorhombic
Pca21
18.7188(3)
26.1144(5)
19.8447(3)
90
90
90
9700.7(3)
8
ρcalcg/cm3
1.238
1.197
1.26
1.304
μ/mm-1
0.447
1948
0.528 × 0.451 ×
0.298
Mo Kα (λ = 0.71073)
1.67
1404
0.169 × 0.126 ×
0.109
Cu Kα (λ = 1.54184)
0.435
4096
Mo Kα (λ = 0.71073)
2.532
4032
0.173 × 0.114 ×
0.063
Cu Kα (λ = 1.54184)
4.786 to 61.014
7.492 to 148.994
4.248 to 61.016
7.322 to 148.98
Index ranges
-25 ≤ h ≤ 25, -18 ≤ k
≤ 18, -32 ≤ l ≤ 32
-23 ≤ h ≤ 28, -17 ≤ k
≤ 17, -14 ≤ l ≤ 14
-19 ≤ h ≤ 19, -30 ≤ k
≤ 30, -46 ≤ l ≤ 48
-23 ≤ h ≤ 22, -31 ≤ k
≤ 32, -24 ≤ l ≤ 20
Reflections
collected
145032
36959
242758
87034
Independent
reflections
14918 [Rint =
0.0386, Rsigma =
0.0226]
3694 [Rint = 0.0296,
Rsigma = 0.0148]
15457 [Rint =
0.0536, Rsigma =
0.0282]
17300 [Rint =
0.0773, Rsigma =
0.0557]
14918/198/699
3694/0/308
15457/110/708
17300/7/1168
F(000)
Crystal size/mm3
Radiation
2Θ range for data
collection/°
0.277 × 0.1 × 0.067
Data/restraints/para
meters
Goodness-of-fit on
F2
Final R indexes
[I>=2σ (I)]
1.031
1.06
1.034
1.026
R1 = 0.0497, wR2 =
0.1336
R1 = 0.0261, wR2 =
0.0714
R1 = 0.0460, wR2 =
0.1154
R1 = 0.0486, wR2 =
0.1061
Final R indexes [all
data]
R1 = 0.0697, wR2 =
0.1447
R1 = 0.0271, wR2 =
0.0720
R1 = 0.0730, wR2 =
0.1276
R1 = 0.0855, wR2 =
0.1253
Largest diff.
peak/hole / e Å-3
0.46/-0.24
0.21/-0.21
0.60/-0.37
0.34/-0.42
Flack Parameter
-
-
-
0.003(6)
Table S3: Crystal data and structure refinement details for compounds 6Li, [perylene][K(DME)4], 7Li and
7K.
Identification code
CCDC Number
Empirical formula
Formula weight
Temperature/K
Crystal system
Space group
a/Å
b/Å
c/Å
α/°
β/°
γ/°
Volume/Å3
Z
8Li
2326098
C74H88Li4Ni2O8
1250.62
100.01(10)
triclinic
P-1
18.8977(2)
19.4534(2)
22.3454(4)
80.1410(10)
87.6060(10)
89.5510(10)
8086.34(19)
4
8K
2326099
C37H50K2NiO7
743.68
100.15
monoclinic
I2/a
26.5914(4)
15.6226(2)
19.9575(3)
90
98.4080(10)
90
8201.8(2)
8
9Li
2326100
C45H61Li2NO5Ni
768.53
173.01(10)
monoclinic
P21/n
10.61066(4)
10.14415(4)
39.27151(16)
90
94.5490(4)
90
4213.72(3)
4
ρcalcg/cm3
1.027
1.205
1.211
μ/mm-1
F(000)
Crystal size/mm3
Radiation
2Θ range for data
collection/°
0.51
2656
0.197 × 0.154 × 0.046
Mo Kα (λ = 0.71073)
0.717
3152
0.393 × 0.243 × 0.168
Mo Kα (λ = 0.71073)
1.001
1648
0.236 × 0.174 × 0.076
Cu Kα (λ = 1.54184)
4.208 to 60.068
4.334 to 60.068
4.514 to 148.988
-26 ≤ h ≤ 26, -27 ≤ k ≤ 27,
-31 ≤ l ≤ 31
486489
-37 ≤ h ≤ 37, -22 ≤ k ≤ 22,
-28 ≤ l ≤ 28
121855
-10 ≤ h ≤ 13, -12 ≤ k ≤ 12,
-49 ≤ l ≤ 49
87197
Independent reflections
47321 [Rint = 0.0640,
Rsigma = 0.0441]
12004 [Rint = 0.0359,
Rsigma = 0.0196]
8616 [Rint = 0.0237, Rsigma
= 0.0117]
Data/restraints/parameter
s
47321/461/1816
12004/80/487
8616/0/491
Goodness-of-fit on F2
1.035
1.036
1.057
Final R indexes [I>=2σ (I)]
R1 = 0.0534, wR2 =
0.1316
R1 = 0.0370, wR2 =
0.0933
R1 = 0.0388, wR2 =
0.1080
Final R indexes [all data]
R1 = 0.0848, wR2 =
0.1440
R1 = 0.0460, wR2 =
0.0970
R1 = 0.0402, wR2 =
0.1092
Largest diff. peak/hole / e
Å-3
0.84/-0.53
0.71/-0.34
0.49/-0.38
Index ranges
Reflections collected
Table S4: Crystal data and structure refinement details for compounds 8Li, 8K and 9Li.
Identification code
CCDC Number
Empirical formula
Formula weight
Temperature/K
Crystal system
Space group
a/Å
b/Å
c/Å
α/°
β/°
γ/°
Volume/Å3
Z
10Li
2326101
C76H90Li4N2Ni2O6
1272.67
100.00(10)
monoclinic
P21/n
13.77390(10)
19.3181(2)
14.30610(10)
90
93.2280(10)
90
3800.61(6)
2
11Li
2326102
C74H88Li4Ni2O8
1250.62
100.01(10)
triclinic
P-1
18.8977(2)
19.4534(2)
22.3454(4)
80.1410(10)
87.6060(10)
89.5510(10)
8086.34(19)
4
ρcalcg/cm3
1.112
1.027
μ/mm-1
F(000)
Crystal size/mm3
Radiation
0.543
1352
0.261 × 0.159 × 0.108
Mo Kα (λ = 0.71073)
0.51
2656
0.197 × 0.154 × 0.046
Mo Kα (λ = 0.71073)
2Θ range for data collection/°
4.216 to 60.444
4.208 to 60.068
-19 ≤ h ≤ 19, -27 ≤ k ≤ 27, -20 ≤ l ≤
20
225483
-26 ≤ h ≤ 26, -27 ≤ k ≤ 27, -31 ≤ l ≤
31
486489
Independent reflections
11310 [Rint = 0.0408, Rsigma =
0.0151]
47321 [Rint = 0.0640, Rsigma =
0.0441]
Data/restraints/parameters
11310/76/444
47321/461/1816
Goodness-of-fit on F2
1.049
1.035
Final R indexes [I>=2σ (I)]
R1 = 0.0394, wR2 = 0.1053
R1 = 0.0534, wR2 = 0.1316
Final R indexes [all data]
R1 = 0.0447, wR2 = 0.1079
R1 = 0.0848, wR2 = 0.1440
Largest diff. peak/hole / e Å-3
0.92/-0.31
0.84/-0.53
Index ranges
Reflections collected
Table S5: Crystal data and structure refinement details for compounds 10Li and 11Li.
Solid-State Structure of [(ttt-CDT)NiPh][Li(12-crown-4)2] (1)
Figure S9: Solid-state structure of [(ttt-CDT)NiPh][Li(12-crown-4)2] (1). Thermal ellipsoids shown at 30%
probability. Hydrogen atoms and disordered components removed and coordinated 12-crown-4 shown
as wireframes for clarity. Selected bond lengths [Å]: Ni1–C1 2.024(1); Ni1–C7 2.077(2); Ni1–C8
2.056(2); Ni1–C11 2.106(2); Ni1–C12 2.087(2); Ni1–C15 2.114(2); Ni1–C16 2.083(2); C7–C8 1.384(3);
C11–C12 1.386(3); C15–C16 1.384(3).
Solid-State Structure of Li4(TMEDA)2(Et2O)2Ph4Ni2(µ;η2;η2-C6H4) (3)
Figure S10: Solid-state structure of Li4(TMEDA)2(Et2O)2Ph4Ni2(µ;η2;η2-C6H4) (3). Thermal ellipsoids
shown at 30% probability. Hydrogen atoms and disordered components removed and coordinated
TMEDA and Et2O shown as wireframes for clarity. Selected bond lengths [Å]: Ni1–C1 1.975(1); Ni1–C7
1.983(1); Ni2–C33 1.973(1); Ni2–C39 1.971(1); Ni1–C19 1.946(1); Ni1–C20 1.966(1); Ni2–C19 1.952(1);
Ni2–C20 1.955(1); Ni1–Ni2 2.8538(6); C19–C20 1.424(2).
Solid-State Structure of Li2(THF)4Ph2Ni(η2-anthracene) (4Li)
Figure S11: Solid-state structure of Li2(THF)4Ph2Ni(η2-anthracene) (4Li). Thermal ellipsoids shown at
30% probability. Hydrogen atoms and disordered components removed and coordinated THF shown as
wireframes for clarity. Selected bond lengths [Å]: Ni1–C1 1.966(2); Ni1–C7 1.945(2); Ni1–C13 1.984(2);
Ni1–C26 1.986(2); C13–C16 1.462(2).
Solid-State Structure of Na2(TMEDA)2Ph2Ni(η2-anthracene) (4Na)
Figure S12: Solid-state structure of Na2(TMEDA)2Ph2Ni(η2-anthracene) (4Na). Thermal ellipsoids shown
at 30% probability. Hydrogen atoms and disordered components removed and coordinated TMEDA
shown as wireframes for clarity. Selected bond lengths [Å]: Ni1–C1 1.964(2); Ni1–C7 1.949(1); Ni1–C25
2.057(2); Ni1–1.954(2); C25–C26 1.449(2).
Solid-State Structure of K2(PMDETA)2Ph2Ni(η2-anthracene) (4K)
Figure S13: Solid-state structure of K2(PMDETA)2Ph2Ni(η2-anthracene) (4K). Thermal ellipsoids shown
at 30% probability. Hydrogen atoms and disordered components removed and coordinated PMDETA
shown as wireframes for clarity. Selected bond lengths [Å]: Ni1–C10 1.946(3); Ni1–C16 2.124(3); Ni1–
C30 1.886(4); Ni1–C43 2.054(5); C30–C43 1.397(7).
Solid-State Structure of Li2(THF)4Ph2Ni(η2-phenanthrene) (5Li)
Figure S14: Solid-state structure of Li2(THF)4Ph2Ni(η2-phenanthrene) (5Li). Thermal ellipsoids shown at
30% probability. Hydrogen atoms and disordered components removed and coordinated THF shown as
wireframes for clarity. Selected bond lengths [Å]: Ni1–C1 1.955(1); Ni1–C7 1.952(2); Ni1–C13 1.983(2);
Ni1–C14 1.976(1); C13–C14 1.453(2).
Solid-State Structure of [Na2(THF)3Ph2Ni(η2-phenanthrene)]2 (5Na)
Figure S15: Solid-state structure of [Na2(THF)3Ph2Ni(η2-phenanthrene)]2 (5Na). Thermal ellipsoids
shown at 30% probability. Hydrogen atoms and disordered components removed and coordinated THF
shown as wireframes for clarity. Only one molecule of the asymmetric unit is displayed. Selected bond
lengths [Å]: Ni1–C1 1.950(2); Ni1–C7 1.948(2); Ni1–C13 1.976(2); Ni1–C14 1.987(2); C13–C14
1.452(3).
Solid-State Structure of [K2(THF)1Ph2Ni(η2-phenanthrene)]∞ (5K)
Figure S16: Solid-state structure of [K2(THF)1Ph2Ni(η2-phenanthrene)]∞ (5Na). Thermal ellipsoids shown
at 30% probability. Hydrogen atoms and disordered components removed and coordinated THF shown
as wireframes for clarity. Selected bond lengths [Å]: Ni1–C15 1.976(3); Ni1–C21 1.946(3); Ni1–C1
2.013(3); Ni1–C2 1.971(3); C1–C2 1.447(4).
Solid-State Structure of [Li(THF)2Ph2Ni(η3-perylene)][Li(THF)4] (6Li)
Figure S17: Solid-state structure of [Li(THF)2Ph2Ni(η3-perylene)][Li(THF)4] (6Li). Thermal ellipsoids
shown at 30% probability. Hydrogen atoms and disordered components removed and coordinated THF
shown as wireframes for clarity. Selected bond lengths [Å]: Ni1–C1 1.944(2); Ni1–C7 1.954(2); Ni1–C13
2.171(2); Ni1–C14 1.977(2); Ni1–C15 2.088(2); C13–C14 1.401(3); C14–C15 1.413(3).
Solid-State Structure of [perylene][K(DME)4]
Figure S18: Solid-state structure of [perylene][K(DME)4]. Thermal ellipsoids shown at 30% probability.
Hydrogen atoms removed and coordinated DME shown as wireframes for clarity. During the preparation
of this manuscript, an identical crystal structure of [perylene][K(DME)4] was also reported by Balashova
and co-workers.12
Solid-State Structure of [Li(THF)2Ph2Ni(η2-coronene)][Li(THF)4] (7Li)
Figure S19: Solid-state structure of [Li(THF)2Ph2Ni(η2-coronene)][Li(THF)4] (7Li). Thermal ellipsoids
shown at 30% probability. Hydrogen atoms and disordered components removed and coordinated THF
shown as wireframes for clarity. Selected bond lengths [Å]: Ni1–C1 1.960(2); Ni1–C7 1.957(2); Ni1–C13
1.983(2); Ni1–C14 2.005(2); C13–C14 1.460(2).
Solid-State Structure of K2(DME)4Ph2Ni(η2-coronene) (7K)
Figure S20: Solid-state structure of K2(DME)4Ph2Ni(η2-coronene) (7K). Thermal ellipsoids shown at 30%
probability. Hydrogen atoms and disordered components removed and coordinated DME shown as
wireframes for clarity. Only one molecule in the asymmetric unit is displayed. Selected bond lengths [Å]:
Ni1–C41 1.937(6); Ni1–C47 1.936(6); Ni1–C1 1.986(6); Ni1–C2 1.989(7); C1–C2 1.48(1).
Solid-State Structure of [Li2(THF)3Ph2Ni(η2-Ph2CO)]2 (8Li)
Figure S21: Solid-state structure of [Li2(THF)3Ph2Ni(η2-Ph2CO)]2 (8Li). Thermal ellipsoids shown at 30%
probability. Hydrogen atoms and disordered components removed and coordinated THF and phenylsubstituents of Ph2CO shown as wireframes for clarity. Only one molecule in the asymmetric unit is
displayed. Selected bond lengths [Å]: Ni3–C71 1.897(2); Ni3–C77 1.970(2); Ni3–C91 1.919(2); Ni3–O11
1.928(1); C91–O11 1.391(2); Ni4–C125 1.956(2); Ni4–C131 1.892(2); Ni4–C112 1.916(2); Ni4–O13
1.924(1); C112–O13 1.389(2).
Solid-State Structure of [K2(DME)3Ph2Ni(η2-Ph2CO)]2 (8K)
Figure S22: Solid-state structure of [K2(DME)3Ph2Ni(η2-Ph2CO)]2 (8K). Thermal ellipsoids shown at 30%
probability. Hydrogen atoms and disordered components removed and coordinated DME and phenylsubstituents of Ph2CO shown as wireframes for clarity. Selected bond lengths [Å]: Ni1–C1 1.929(1); Ni1–
C7 1.880(1); Ni1–C13 1.929(2); Ni1–O1 1.928(1); C13–O1 1.375(2).
Solid-State Structure of Li2(THF)5Ph2Ni(η2-PhCH=NPh) (9Li)
Figure S23: Solid-state structure of Li2(THF)5Ph2Ni(η2-PhCH=NPh) (9Li). Thermal ellipsoids shown at
30% probability. Hydrogen atoms removed and coordinated THF shown as wireframes for clarity.
Selected bond lengths [Å]: Ni1–C14 1.929(1); Ni1–C20 1.966(1); Ni1–C1 1.925(1); Ni1–N1 1.956(1);
C1–N1 1.419(2).
Solid-State Structure of [Li2(THF)3Ph2Ni(η2-Ph2CHCN)]2 (10Li)
Figure S24: Solid-state structure of [Li2(THF)3Ph2Ni(η2-Ph2CHCN)]2 (10Li). Thermal ellipsoids shown at
30% probability. Hydrogen atoms and disordered components removed and coordinated THF and
phenyl-substituents of Ph2CHCN shown as wireframes for clarity. Selected bond lengths [Å]: Ni1–C1
1.986(1); Ni1–C7 1.932(1); Ni1–C13 1.839(1); Ni1N1 1.954(2); C13–N1 1.242(2).
Solid-State Structure of Li(THF)3(PPh3)2(CO)3Ni2(µ-PPh2) (11Li)
Figure S25: Solid-state structure of Li(THF)3(PPh3)2(CO)3Ni2(µ-PPh2) (11Li). Thermal ellipsoids shown
at 30% probability. Hydrogen atoms and disordered components removed and coordinated THF and
phenyl-substituents shown as wireframes for clarity. Selected bond lengths [Å]: Ni1–P1 2.1928(6); Ni1–
C1 1.757(2); C1–O1 1.150(3); Ni1–P2 2.2245(4); Ni1–C2 1.902(2); C2–O2 1.187(2); Ni1–Ni2 2.4845(4);
Ni2–P2 2.2257(5); Ni2–C2 1.902(2); Ni2–C3 1.746(2); C3–O3 1.154(3); Ni2–P3 2.1967(6).
NMR Spectra of Reported Compounds
Spectra S1: 1H NMR spectrum of PhLi(Et2O)0.02 in THF-d8.
Spectra S2: 7Li NMR spectrum of PhLi(Et2O)0.02 in THF-d8.
Spectra S3: 1H NMR spectrum of [(ttt-CDT)NiPh][Li(12-crown-4)2] (1) in THF-d8 at -20 °C.
Spectra S4: 7Li NMR spectrum of [(ttt-CDT)NiPh][Li(12-crown-4)2] (1) in THF-d8 at -20 °C.
Spectra S5: 13C{1H} NMR spectrum of [(ttt-CDT)NiPh][Li(12-crown-4)2] (1) in THF-d8 at -20 °C.
Spectra S6: 1H NMR spectrum of Li2(TMEDA)2Ph2Ni(η2-CDT) (2) in THF-d8.
Spectra S7: 7Li NMR spectrum of Li2(TMEDA)2Ph2Ni(η2-CDT) (2) in THF-d8.
Spectra S8: 13C{1H} NMR spectrum of Li2(TMEDA)2Ph2Ni(η2-CDT) (2) in THF-d8.
Spectra S9: 1H NMR spectrum of Li4(TMEDA)2(Et2O)2Ph4Ni2(µ;η2;η2-C6H4) (3) in THF-d8.
Spectra S10: 7Li NMR spectrum of Li4(TMEDA)2(Et2O)2Ph4Ni2(µ;η2;η2-C6H4) (3) in THF-d8.
Spectra S11: 13C{1H} NMR spectrum of Li4(TMEDA)2(Et2O)2Ph4Ni2(µ;η2;η2-C6H4) (3) in THF-d8.
Spectra S12: 1H NMR spectrum of Li2(THF)4Ph2Ni(η2-anthracene) (4Li) in THF-d8. * Unidentified
impurity.
Spectra S13: 7Li NMR spectrum of Li2(THF)4Ph2Ni(η2-anthracene) (4Li) in THF-d8.
Spectra S14: 13C{1H} NMR spectrum of Li2(THF)4Ph2Ni(η2-anthracene) (4Li) in THF-d8.
Spectra S15: 1H NMR spectrum of Na2(TMEDA)2Ph2Ni(η2-anthracene) (4Na) in THF-d8. * Unidentified
impurity.
Spectra S16: 13C{1H} NMR spectrum of Na2(TMEDA)2Ph2Ni(η2-anthracene) (4Na) in THF-d8. * C6H6.
Spectra S17: 1H NMR spectrum of K2(PMDETA)2Ph2Ni(η2-anthracene) (4K) in THF-d8.
Spectra S18: 13C{1H} NMR spectrum of K2(PMDETA)2Ph2Ni(η2-anthracene) (4K) in THF-d8.
Spectra S19: 1H NMR spectrum of Li2(THF)4Ph2Ni(η2-phenanthrene) (5Li) in THF-d8.
Spectra S20: 7Li NMR spectrum of Li2(THF)4Ph2Ni(η2-phenanthrene) (5Li) in THF-d8.
Spectra S21: 13C{1H} NMR spectrum of Li2(THF)4Ph2Ni(η2-phenanthrene) (5Li) in THF-d8.
Spectra S22: 1H NMR spectrum of [Na2(THF)3Ph2Ni(η2-phenanthrene)]2 (5Na) in THF-d8. * Residual
Et2O.
Spectra S23: 13C{1H} NMR spectrum of [Na2(THF)3Ph2Ni(η2-phenanthrene)]2 (5Na) in THF-d8.
Spectra S24: 1H NMR spectrum of [K2(THF)1Ph2Ni(η2-phenanthrene)]∞ (5K) in THF-d8. * Residual Et2O
and pentane.
Spectra S25: 13C{1H} NMR spectrum of [K2(THF)1Ph2Ni(η2-phenanthrene)]∞ (5K) in THF-d8.
Spectra S26: 1H NMR spectrum of [Li(THF)2Ph2Ni(η3-perylene)][Li(THF)4] (6Li) in THF-d8.
Spectra S27: 7Li NMR spectrum of [Li(THF)2Ph2Ni(η3-perylene)][Li(THF)4] (6Li) in THF-d8.
Spectra S28: 13C{1H} NMR spectrum of [Li(THF)2Ph2Ni(η3-perylene)][Li(THF)4] (6Li) in THF-d8.
Spectra S29: 1H NMR spectrum of [Li(THF)2Ph2Ni(η2-coronene)][Li(THF)4] (7Li) in THF-d8 at -20 °C.
Spectra S30: 7Li NMR spectrum of [Li(THF)2Ph2Ni(η2-coronene)][Li(THF)4] (7Li) in THF-d8 at -40 °C.
Spectra S31: 13C{1H} NMR spectrum of [Li(THF)2Ph2Ni(η2-coronene)][Li(THF)4] (7Li) in THF-d8 at -20 °C.
Spectra S32: 1H NMR spectrum of K2(DME)4Ph2Ni(η2-coronene) (7K) in THF-d8.
Spectra S33: Stacked 1H NMR spectra of [Li2(THF)3Ph2Ni(η2-Ph2CO)]2 (8Li) in THF-d8 at -20 °C (blue
trace) and +20 °C (red trace). * Residual Et2O.
Spectra S34: Stacked 7Li NMR spectra of [Li2(THF)3Ph2Ni(η2-Ph2CO)]2 (8Li) in THF-d8 at -20 °C (blue
trace) and +20 °C (red trace). * Unidentified impurities.
Spectra S35: 13C{1H} NMR spectra of [Li2(THF)3Ph2Ni(η2-Ph2CO)]2 (8Li) in THF-d8 at -20 °C.
Spectra S36: 1H NMR spectrum of [K2(DME)3Ph2Ni(η2-Ph2CO)]2 (8K) in THF-d8.
Spectra S37: 13C{1H} NMR spectrum of [K2(DME)3Ph2Ni(η2-Ph2CO)]2 (8K) in THF-d8.
Spectra S38: 1H NMR spectrum of Li2(THF)5Ph2Ni(η2-PhCH=NPh) (9Li) in THF-d8.
Spectra S39: 7Li NMR spectrum of Li2(THF)5Ph2Ni(η2-PhCH=NPh) (9Li) in THF-d8.
Spectra S40: 13C{1H} NMR spectrum of Li2(THF)5Ph2Ni(η2-PhCH=NPh) (9Li) in THF-d8.
Spectra S41: 1H NMR spectrum of [Li2(THF)3Ph2Ni(η2-Ph2CHCN)]2 (10Li) in THF-d8 at -20 °C. *
Unidentified impurities/decomposition products.
Spectra S42: 7Li NMR spectrum of [Li2(THF)3Ph2Ni(η2-Ph2CHCN)]2 (10Li) in THF-d8 at -20 °C.
Spectra S43: 1H NMR spectrum of Li(THF)3(PPh3)2(CO)3Ni2(µ-PPh2) (11Li) in THF-d8.
Spectra S44: 7Li NMR spectrum of Li(THF)3(PPh3)2(CO)3Ni2(µ-PPh2) (11Li) in THF-d8.
Spectra S45: 31P NMR spectrum of Li(THF)3(PPh3)2(CO)3Ni2(µ-PPh2) (11Li) in THF-d8.
Spectra S46: 13C{1H} NMR spectrum of Li(THF)3(PPh3)2(CO)3Ni2(µ-PPh2) (11Li) in THF-d8.
Reference Spectra
Spectra S47: 1H NMR spectrum of phenanthrene in THF-d8. 1H NMR (300.1 MHz, THF-d8): δ 8.75 (dd, J
= 7.9, 1.2 Hz, 2H), 7.89 (m, 2H), 7.74 (s, 2H), 7.66–7.53 (m, 4H).
Spectra S48: 13C{1H} NMR spectrum of phenanthrene in THF-d8. 13C{1H} NMR (75.5 MHz, THF-d8): δ
133.3, 131.5, 129.5, 127.8, 127.5, 127.5, 123.7.
Spectra S49: 1H NMR spectrum of N-benzylideneaniline in THF-d8. 1H NMR (300.1 MHz, THF-d8): δ
8.50 (s, 1H), 7.96–7.88 (m, 2H), 7.48–7.41 (m, 3H), 7.38–7.31 (m, 2H), 7.24–7.14 (m, 3H).
Spectra S50: 13C{1H} NMR spectrum of N-benzylideneaniline in THF-d8. 13C{1H} NMR (75.5 MHz, THFd8): δ 160.8, 153.4, 137.9, 132.1, 129.9, 129.7, 129.6, 126.7, 121.8.
Spectra S51: 1H NMR spectrum of diphenylacetonitrile in THF-d8. 1H NMR (300.1 MHz, THF-d8): δ
7.41–7.24 (m, 10H), 5.42 (s, 1H).
Spectra S52: 13C{1H} NMR spectrum of diphenylacetonitrile in THF-d8. 13C{1H} NMR (75.5 MHz, THFd8): δ 138.2, 130.0, 128.9, 128.7, 120.4, 42.9.
In Situ Synthesis and Characterisation of Imine Addition Product, Ph2CHN(Li)Ph
N-benzylideneaniline (18.1 mg, 0.1 mmol) was dissolved in THF-d8 (0.5 mL) and cooled to -30 °C. PhLi
(8.6 mg, 0.1 mmol) was added and the colourless solution was warmed to room temperature. 1H NMR
spectroscopy indicated clean nucleophilic addition of PhLi across the C=N bond to give Ph2CHN(Li)Ph.
Spectra S53: 1H NMR spectrum of Ph2CHN(Li)Ph prepared in situ in THF-d8. 1H NMR (300.1 MHz, THFd8): δ 7.28 (m, 4H, Ph2-o-CH), 7.15 (t, J = 7.6 Hz, 4H, Ph2-m-CH), 7.03 (tt, J = 7.2, 1.4 Hz, 2H, Ph2-pCH), 6.61 (dd, J = 7.1, 1.6 Hz, 2H, N-Ph-m-CH), 6.00 (br d, J = 7.0 Hz, 2H, N-Ph-o-CH), 5.74 (tt, J = 7.0,
1.0 Hz, 1H, N-Ph-p-CH), 5.25 (s, 1H, CH).
Spectra S54: 7Li NMR spectrum of Ph2CHN(Li)Ph prepared in situ in THF-d8. 7Li NMR (116.6 MHz,
THF-d8): δ 0.63 (s).
Spectra S55: 13C{1H} NMR spectrum of Ph2CHN(Li)Ph prepared in situ in THF-d8. 13C{1H} NMR (75.5
MHz, THF-d8): δ 161.8 (N-Ph-ipso-C), 150.7 (Ph2-ipso-C), 129.2 (Ph2-o-CH), 129.0 (br, N-Ph-m-CH),
128.6 (Ph2-m-CH), 126.0 (Ph2-p-CH), 113.9 (br, N-Ph-o-CH), 106.9 (N-Ph-p-CH), 68.5 (CH).
In Situ Synthesis and Characterisation of Lithiated Diphenylketenimine, Ph2C=C=N–Li
Diphenylacetonitrile (19.3 mg, 0.1 mmol) was dissolved in THF-d8 (0.5 mL) and cooled to -30 °C. PhLi (8.6
mg, 0.1 mmol) was added leading to a colour change from colourless to pale yellow upon warming to room
temperature.
H NMR spectroscopy indicated the clean α-deprotonation to give the lithiated
1
diphenylketenimine alongside benzene.
Spectra S56: 1H NMR spectrum of lithiated diphenylketenimine prepared in situ in THF-d8. 1H NMR
(300.1 MHz, THF-d8): δ 7.23 (dd, J = 7.4, 1.2 Hz, 4H, Ph-o-CH), 6.88 (m, 4H, Ph-m-CH), 6.36 (tt, J = 7.1,
1.2 Hz, 2H, Ph-p-CH).
Spectra S57: 7Li NMR spectrum of lithiated diphenylketenimine prepared in situ in THF-d8. 7Li NMR
(116.6 MHz, THF-d8): δ -0.27 (s).
Spectra S58: 13C{1H} NMR spectrum of lithiated diphenylketenimine prepared in situ in THF-d8. 13C{1H}
NMR (75.5 MHz, THF-d8): δ 145.4 (Ph-ipso-C), 140.0 (C=C=N), 128.4 (Ph-m-CH), 122.2 (Ph-o-CH),
116.6 (Ph-p-CH), 54.6 (C=C=N).
References
(1)
Borys, A. M. The Schlenk Line Survival Guide https://schlenklinesurvivalguide.com. (Accessed
March 2024)
(2)
Borys, A. M. An Illustrated Guide to Schlenk Line Techniques. Organometallics 2023, 42 (3), 182–
196. https://doi.org/10.1021/acs.organomet.2c00535.
(3)
Bogdanović, V. B.; Kröner, M.; Wilke, G. Olefin Complexes of Nickel(0). Liebigs Ann. Chem 1966,
669 (1), 1–23. https://doi.org/10.1002/jlac.19666990102.
(4)
Borys, A. M.; Hevia, E. The Anionic Pathway in the Nickel‐Catalysed Cross‐Coupling of Aryl Ethers.
Angew. Chem. Int. Ed. 2021, 60 (46), 24659–24667. https://doi.org/10.1002/anie.202110785.
(5)
Neufeld, R.; Stalke, D. Accurate Molecular Weight Determination of Small Molecules via DOSYNMR by Using External Calibration Curves with Normalized Diffusion Coefficients. Chem. Sci. 2015,
6 (6), 3354–3364. https://doi.org/10.1039/c5sc00670h.
(6)
Bachmann, S.; Gernert, B.; Stalke, D. Solution Structures of Alkali Metal Cyclopentadienides in THF
Estimated by ECC-DOSY NMR-Spectroscopy. Chem. Commun. 2016, 52 (87), 12861–12864.
https://doi.org/10.1039/c6cc07273a.
(7)
Bachmann, S.; Neufeld, R.; Dzemski, M.; Stalke, D. New External Calibration Curves (ECCs) for
the Estimation of Molecular Weights in Various Common NMR Solvents. Chem. Eur. J. 2016, 22
(25), 8462–8465. https://doi.org/10.1002/chem.201601145.
(8)
Oxford-Diffraction. CrysAlisPro. Oxford Diffraction 2018.
(9)
Sheldrick, G. M. A Short History of SHELX. Acta Cryst. 2008, 64 (1), 112–122.
https://doi.org/10.1107/S0108767307043930.
(10)
Sheldrick, G. M. Crystal Structure Refinement with SHELXL. Acta Cryst. 2015, C71, 3–8.
https://doi.org/10.1107/S2053229614024218.
(11)
Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. OLEX2: A
Complete Structure Solution, Refinement and Analysis Program. J. Appl. Crystallogr. 2009, A42 (2),
339–341. https://doi.org/10.1107/S0021889808042726.
(12)
Balashova, T. V; Polyakova, S. K.; Ilichev, V. A.; Baranov, E. V; Fukin, G. K.; Kozhanov, K. A.;
Zhigulin, G. Y.; Ketkov, S. Y.; Bochkarev, M. N. Synthesis and Structure of a Samarium Complex
with Perylene. Organometallics 2023. https://doi.org/10.1021/acs.organomet.3c00388.