Dalton Transactions
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ether using a separating funnel. The ethereal phase was col- Hz, Rh–η2(Si–H)). HMQC 103Rh–1H{31P} NMR: (19.12 MHz,
lected, dried over MgSO4 and finally evaporated to dryness. C7D8) δ: −8738 (s).
The yellowish powder was further purified by recrystallization
Synthesis of compound [Ir2(µ-Cl)2P{[η2-(H-SiMe2)
CH2C6H4][(o-C6H4)CH2SiMe2]2}], 2Ir
from hot ethanol solutions at 263 K to yield a white solid in
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89%, and its purity was verified by m.p. and H and 31P NMR.
P{(o-C6H4)CH3}3 (1 g, 3.3 mmol) was dissolved in 30 mL of
In a Schlenk flask, compound 1 (71 mg, 0.15 mmol) and
hexane, and then TMEDA (1.48 mL, 9.9 mmol) and titrated
[IrCl(COD)]2 (50 mg, 0.07 mmol) were degassed and then dis-
hexane solution of nBuLi (3.96 mL, 9.9 mmol) were added.
solved in pentane (1.5 mL). The solution was stirred for two
After stirring for 20 h, the bright orange red reaction mixture
hours at room temperature after which it was concentrated
was cooled to 195 K and excess ClSiMe2H (3 mL, 27 mmol)
and kept overnight at 236 K. The resulting yellow solid was
was added via syringe. The off-white suspension was allowed
washed twice with 0.5 mL of cold pentane to yield a light
to warm up to room temperature and kept under stirring for
yellow solid. Yield 97% (103 mg). IR (KBr): ν(Ir⋯H–Si)
12 h, after which the solvent was removed by distillation under
2019 cm−1, ω(Si–H) 796 cm−1. 1H NMR (400 MHz, C6D6, 293 K)
a reduced pressure. The white solid was dissolved in 15 mL of
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δ: 6.99 (tt, JP–H 1.6 Hz, JH–H 1.6 Hz; JH–H 7.6 Hz, 6H,
hexane and recrystallized overnight at 263 K. Yield 91% from
P{(o-C6H4)CH3}3. M.p. 375 K. Anal. Calcd for C27H39PSi3: C,
67.73; H, 8.21. Found: C, 67.70; H, 8.15. 1H NMR (C6D6,
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CHaromatic), 6.93 (dd, JP–H 11.2 Hz; JH–H 7.6 Hz, 6H,
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CHaromatic), 6.86 (pt, JH–H 5.6 Hz, 6H, CHaromatic), 6.73 (dt,
4JP–H 1.6 Hz, JH–H 7.6 Hz, 6H, CHaromatic), 2.13 (d, JH–H 14.4
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2
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400 MHz, 293 K): δ 7.04 (tt, JH–H 7.7 Hz, JH–H 1.14 Hz, 3H),
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Hz, 6H, CH2), 2.05 (dd, JH–H 14.4 Hz; JP–H 3.2 Hz, 6H, CH2),
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7.01 (m, 6H), 6.82 (t, JH–H 7 Hz, 3H), 4.26 (nd, JH–H 3.6 Hz,
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0.55 (br. s, JSi–H 42.0 Hz, 2H, σ(SiH)), 0.41 (s, 18H, CH3), 0.53
5JP–H 1.8 Hz, JSi–H 189 Hz satellites, 3H), 2.38 (br. s, 6H), 0.08
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(s, 18H, CH3). 13C{1H} NMR (C6D6, 175 MHz, 293 K) δ: 147.3
(d, JH–H 3.6 Hz, 18H). 13C{1H} NMR (175 MHz, C6D6) δ 145.1
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(d, JP–C 13.5 Hz, Cipso–P), 132.5 (d, JP–C 5.6 Hz, Cipso–C), 131.6
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(d, JP–C 26.3 Hz), 134.1 (s), 133.7 (d, JP–C 10.5 Hz), 129.0 (d,
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(d, JP–C 1.75 H, CHaromatic), 131.5 (d, JP–C 8.93 Hz, CHaromatic),
128.6 (s, CHaromatic), 125.3 (d, 3JP–C 8.75 Hz, CHaromatic), 27.6 (d,
3JP–C 11.4 Hz, CH2), 2.22 (s, CH3), 2.93 (s, CH3). 31P{1H} NMR
(161.9 MHz, C6D6, 293 K) δ: 0.21 (s).
2JP–C 5.3 Hz), 128.7 (s), 125.1 (s), 23.4 (d, JP–C 19.3 Hz, CH2),
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−4.25 (s, CH3, JSi–C 50.8 Hz, satellites). 31P{1H} NMR
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(161.9 MHz, C6D6) δ −27.0. 29Si{1H} NMR (75.54 MHz, C6D6)δ
−12.1 (s). IR (KBr disc) 2119 cm−1 (s, νSi–H), 1247 cm−1
(s, νSi–Me2), 887 cm−1 (s, ωSi–H).
Synthesis of [Rh2(μ-Cl)2{P((o-C6H4)CH2SiMe2)3}2]2O, 3Rh
Reaction of 2Rh with adventitious water present in a toluene/
Et2O mixture led to the formation of yellow crystals which were
filtrated and subsequently dried under vacuum. They were
Synthesis of [Rh2(µ-Cl)2P{[η2-(H-SiMe2)CH2C6H4][(o-C6H4)
CH2SiMe2]2}], 2Rh
In a Schlenk flask, compound 1 (215 mg, 0.45 mmol) and soluble in most laboratory solvents. Anal. Calcd for
[RhCl(COD)]2 (110 mg, 0.22 mmol) were degassed and then C54H72Cl2OP2Rh2Si6: C, 52.14; H, 5.79. Found: C, 51.56; H,
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dissolved in toluene-d8 (1.5 mL). The solution was stirred for 5.39. H NMR (400 MHz, C6D6, 293 K) δ: 7.59 ppm (dd, JH–H
two hours at room temperature after which it was concentrated 7.2 Hz, 3JH–P 4.9 Hz, 1H, CH), 7.14–6.94 (m, 5H, CH), 6.94–6.87
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and kept overnight at 236 K. The resulting yellow solid was (m, 1H, CH), 6.77 (t, JH–H 7.4 Hz, 1H, CH), 6.72–6.60 (m, 4H,
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washed twice with 0.5 mL of Et2O to yield a light brown solid. CH), 3.63 (d, JH–H 14.2 Hz, 1H, CH2), 3.36 (d, JH–H 13.9 Hz,
Yield 83% (91 mg). Anal. Calcd for C54H74Cl2P2Rh2Si6: C, 1H, CH2), 2.89 (dd, 2JH–H 14.5, 4JH–P 3.0 Hz, 1H, CH2), 2.33 (dd,
52.72; H, 6.06. Found: C, 52.96; H, 6.10. 1H NMR (300 MHz, 2JH–H 14.1, JH–P 7.3 Hz, 1H, CH2), 2.01 (d, JH–H 13.8 Hz, 1H,
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C7D8, 293 K): δ 7.10 (br. s, 1H, CH), 7.01 (br. m, 3H, CH), 6.86 CH2), 1.91 (ddd, JH–H 14.2, JH–P 7.1, JH–Rh 2.0 Hz, 1H, CH2),
(br. m, 6H, CH), 6.74 (br. m, 3H, CH), 2.56 (br. d, JH–Rh 6.4 Hz, 1.28 (s, 3H, CH3), 0.65 (s, 3H, CH3), 0.59 (s, 3H, CH3), 0.49 (s,
JH–Si 53.4 Hz from 29Si satellites, 2H, η2-HSi), 2.15 (br ψt, JH–H 3H, CH3), 0.05 (s, 3H, CH3), −0.22 (s, 3H, CH3). 13C{1H} NMR
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16 Hz, 12H, SiCH2), 0.56 (br. s, 12H, SiCH3), 0.32 (s, 24H, (176.048 MHz, C6D6, 293 K) δ: 150.1 (d, JC–P 14.3 Hz, Cipso–C),
SiCH3). 31P{1H} NMR (161.9 MHz, C7D8): δ 27.8 (d, JP–Rh 154 148.2 (d, JC–P 13.6 Hz, Cipso–C), 144.1 (d, JC–P 12.0 Hz, Cipso–C
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Hz). 13C{1H} NMR (100.61 MHz, C7D8, 223 K): δ: 146.8 (t, JC–P η2-SiH), 133.8 (dd, JC–P 16.3 Hz, JC–Rh 4.4 Hz, CHaromatic, 4C),
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12.5 Hz, 2JC–Rh 12.5 Hz, Cipso–P), 144.9 (d, 1JC–P 18.4 Hz, Cipso–P 132.7 (d, JC–P 6.8 Hz, CHaromatic, 2C), 131.7 (d, J
Rh-η2(Si-H)), 135.0 (s, Cipso–C), 135.0 (s, Cipso–C), 131.1 (s, CHaromatic, 2C), 131.3 (s, Cipso–C, 2C), 131.1 (t, J
8.1 Hz,
7.7 Hz,
C–P
C–P
Cipso–C), 131.0–130.8 (overlapped higher order m, CHaromatic), CHaromatic, 4C), 130.9 (s, Cipso–C, 2C), 130.1 (s, Cipso–C, 2C),
130.7 (d, JC–P 4.9 Hz, CHaromatic), 130.5 (d, JC–P 8.0 Hz, 125.6 (d, JC–P 8 Hz, CHaromatic, 2C), 125.4 (dd, JC–P 8.5, JC–Rh 4.9
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CHaromatic), 130.4 (d, JC–P 5.1 Hz, CHaromatic), 125.5 (d, JC–P 6.3 Hz, CHaromatic, 4C), 33.3 (d, JC–P 13.0 Hz, CH2), 32.1 (d,
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Hz, CHaromatic), 124.6(m, CHaromatic), 32.1 (d, JC–P 18.8 Hz, 3JC–P 8.0 Hz, CH2), 28.7 (d, JC–P 13.0 Hz, CH2), 9.55 (s, CH3),
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CH2), 30.8 (d, JC–P 16.2 Hz, CH2), 22.8 (d, JC–P 4.3 Hz, CH2), 5.20 (s, CH3), 4.70 (s, CH3), 3.81 (s, CH3), 3.10 (s, CH3), 2.95 (s,
10.1 (s, CH3), 9.6 (s, CH3), 5.0 (s, CH3), 3.9 (s, CH3), −4.6 (s, CH3). 31P{1H} NMR (161.9 MHz, C6D6, 293 K) δ: 26.20 (d, 1JP–Rh
CH3), −4.8 (s, CH3). DEPT 29Si{1H} NMR(79.49 MHz, C7D8, 157.1 Hz). 29Si{31P} DEPT NMR (79.49 MHz, C6D6, 293 K)
223 K) δ: 57.0 (dd, JSi–Rh 36.7 Hz, JSi–P 10.9 Hz, Rh–Si), 52.9 δ: 67.04 (s), 42.32 (s) and 5.37 (s). 103Rh–1H{31P} HMBC NMR
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(dd, JSi–Rh 38.7 Hz, JSi–P 12.3 Hz, Rh–Si), −10.5 (s, w1/2 10.3 (12.59 MHz, C6D6, 293 K) δ: −8416.73 ppm (s).
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Dalton Trans.