Inorganic Chemistry
Article
× CHAr), 126.2 (d, JPC = 3.0 Hz, CHAr), 127.3 (s, CHAr), 130.0 (s, 2 ×
CHAr), 133.6 (d, JPC = 4.9 Hz, CAr), 136.4 (br d, JPC = 6.9 Hz, 2 ×
CHAr), 140.5 (d, JPC = 0.9 Hz, CAr), 140.6 (br d, JPC = 8.5 Hz, 2 ×
CHAr), 141.7 (d, JPC = 0.6 Hz, CAr), 147.7 (s, CAr), 147.80 (s, CAr),
174.8 (dd, JPC = 10.1 Hz, JRhC = 0.8 Hz, PCCN). 29Si{1H} NMR
(59.63 MHz, THF-d8, 25 °C): δ −50.8 (d, JSiRh = 104.5 Hz, SiRh),
11.7 (d, JSiP = 1.9 Hz, SiMe). 31P{1H} NMR (121.49 MHz, THF-d8, 25
°C): δ 48.6 (s). Minor isomer (8%). 31P{1H} NMR (121.49 MHz,
THF-d8, 25 °C): δ 43.8 (s).
C
tBu), 89.6 (d, JPC = 122.4 Hz, PCCN), 123.5 (s, CHAr), 124.3 (s,
CHAr), 124.9 (s, CHAr), 126.9 (s, 2 × CHAr), 127.4 (d, JPC = 2.8 Hz,
CHAr), 128.2 (s, 2 × CHAr), 128.3 (br, 3 × CHAr), 133.1 (d, JPC = 4.3
Hz, CAr), 135.7 (br, 2 × CHAr), 138.3 (s, CAr), 140.7 (d, JPC = 1.3 Hz,
CAr), 145.0 (s, CAr), 148.1 (s, CAr), 174.9 (d, JPC = 10.2 Hz, PCCN).
29Si{1H} NMR (59.63 MHz, CDCl3, 25 °C): δ −51.5 (s, SiCu), 11.7
(s, J = 12.18 Hz, SiMe). 31P{1H} NMR (121.49 MHz, CDCl3, 25 °C):
δ 45.7 (s). Minor isomer (8%). 31P{1H} NMR (121.49 MHz, CDCl3,
25 °C): δ 41.1 (s).
Silacyclopropylidene-RhICl(CO2)2 Complex (3). In a pressurized
NMR tube, a solution of 2 (40.0 mg, 0.042 mmol) in CDCl3 was
exposed to a CO atmosphere (5 bar). After 5 min of stirring, the
bright-yellow solution of 3 was analyzed by NMR. A solution of 2
(120.0 mg, 0.126 mmol) in CH2Cl2 (2 mL) was put under stirring at
RT. After 10 min of CO bubbling in the solution, the resulting yellow
solid of 3 was used to prepare KBr pellets suitable for IR analysis.
Major isomer (92%) . 1H NMR (300.18 MHz, THF-d8, 25 °C): δ 0.01
(s, 3H, CH3Si), 0.65 (s, 3H, CH3Si), 1.16 (m, 6H, 2 × CH3iPr), 1.29
(d, JHH = 6.7 Hz, 3H, CH3iPr), 1.43 (s, 9H, 3 × CH3tBu), 1.46 (m, 1H,
1/2CH2Norb), 1.62 (overlapped with methyl, 3H, CH3iPr), 1.63
(overlapped with tBu, 1H, 1/2CH2CbridgeheadCP), 1.64 (s, 9H, 3 ×
Silacyclopropylidene-AuICl Complex (5). To a flask containing 1
(24.3 mg, 0.034 mmol) and AuCl(SMe2) (10.1 mg, 0.034 mmol) was
added THF (0.5 mL) at RT. After 15 min of stirring at RT, THF was
removed, and the solid was washed with pentane, to give the
analytically pure 5 as a light-violet powder (29.7 mg, 92%). Crystals of
compound 5 suitable for X-ray diffraction analysis were obtained by
slow crystallization in chloroform at RT. Mp: 240−241 °C. Major
isomer (92%). 1H NMR (300.18 MHz, CDCl3, 25 °C): δ 0.08 (s, 3H,
CH3Si), 0.59 (s, 3H, CH3Si), 1.04 (d, JHH = 6.8 Hz, 3H, CH3iPr), 1.22
(d, JHH = 6.8 Hz, 3H, CH3iPr), 1.26 (overlapped with CH3tBu, 3H,
CH3iPr), 1.27 (s, 9H, 3 × CH3tBu), 1.37 (br d, JHH = 8.5 Hz, 1H,
1/2CH2Norb), 1.49 (m, 1H, 1/2CH2CbridgeheadCP), 1.58 (s, 9H, 3 ×
CH3tBu), 1.68 (br d, JHH = 8.50 Hz, 1H, 1/2CH2Norb), 1.70 (overlapped
with CH3iPr, 1H, 1/2CH2CbridgeheadCP), 1.73 (d, JHH = 6.7 Hz, 3H,
1
1
CH3tBu), 1.78 (m, 2H, /2CH2CbridgeheadCP, /2CH2Norb), 1.91 (m, 2H,
CH2CbridgeheadCN), 2.68 (s, 1H, PCCHbridgehead), 3.28 (sep, JHH = 6.7
Hz, 1H, CHiPr), 3.41 (d, JPH = 30.8 Hz, 1H, SiCH), 3.54 (s, 1H,
NCCHbridgehead), 3.64 (overlapped with THF, 1H, CHiPr), 6.63 (m,
2H, HAr), 6.78 (m, 3H, HAr), 6.97−7.43 (m, 10H, HAr). 13C{1H}
NMR (75.47 MHz, THF-d8, 25 °C): δ 2.5 (d, JPC = 2.1 Hz, CH3Si),
5.3 (d, JPC = 1.1 Hz, CH3Si), 24.0 (s, CH3iPr), 24.1 (s, CH3iPr), 25.5
(br, CH2CbridgeheadCP), 25.6 (s, CH3iPr), 26.1 (s, CH3iPr), 27.8 (s,
CH2CbridgeheadCN), 28.0 (s, CHiPr), 28.6 (m, SiCH), 28.7 (s, CHiPr),
32.2 (d, JPC = 5.1 Hz, 3C, 3 × CH3tBu), 32.8 (d, JPC = 4.6 Hz, 3C, 3 ×
CH3tBu), 44.1 (d, JPC = 8.7 Hz, NCCHbridgehead), 46.8 (d, JPC = 8.2 Hz,
CH2Norb), 47.3 (d, JPC = 10.0 Hz, PCCHbridgehead), 47.9 (d, JPC = 58.0
1
CH3iPr), 1.74 (overlapped with CH3iPr, 1H, /2CH2CbridgeheadCN), 1.88
(m, 1H, /2CH2CbridgeheadCN), 2.63 (s, 1H, PCCHbridgehead), 3.09 (sep,
1
JHH = 6.8 Hz, 1H, CHiPr), 3.28 (sep, JHH = 6.8 Hz, 1H, CHiPr), 3.36 (d,
JPH = 30.4 Hz, 1H, SiCH), 3.39 (s, 1H, NCCHbridgehead), 6.61 (m, 2H,
HAr), 6.90 (m, 3H, HAr), 7.13−7.33 (6H, HAr), 7.72 (br, 2H, HAr).
13C{1H} NMR (75.47 MHz, CDCl3, 25 °C): δ 3.5 (d, JPC = 2.1 Hz,
CH3Si), 6.2 (d, JPC = 0.9 Hz, CH3Si), 23.5 (s, CH3iPr), 24.7 (s,
CH2CbridgeheadCP), 25.0 (s, CH3iPr), 26.0 (s, CH3iPr), 26.3 (s, CH3iPr),
27.7 (s, CH2CbridgeheadCN), 28.0 (s, CHiPr), 28.3 (d, JPC = 3.0 Hz,
SiCH), 28.9 (s, CHiPr), 32.4 (d, JPC = 5.0 Hz, 3C, 3 × CH3tBu), 33.5 (d,
JPC = 4.5 Hz, 3C, 3 × CH3tBu), 44.2 (d, JPC = 8.7 Hz, NCCHbridgehead),
44.5 (d, JPC = 61.4 Hz, PCSi), 47.1 (d, JPC = 9.9 Hz, PCCHbridgehead),
47.4 (d, JPC = 8.1 Hz, CH2Norb), 52.6 (d, JPC = 1.5 Hz, CtBu), 52.9 (s,
CtBu), 90.8 (d, JPC = 120.4 Hz, PCCN), 124.0 (s, CHAr), 124.2 (s,
CHAr), 125.1 (s, CHAr), 127.0 (s, 2 × CHAr), 127.5 (d, JPC = 2.8 Hz,
CHAr), 128.0 (br s, 2 × CHAr), 128.5 (s, CHAr), 128.8 (s, 2 × CHAr),
132.1 (d, JPC = 4.6 Hz, CAr), 135.4 (br, 2 × CHAr), 138.0 (s, CAr),
139.2 (d, JPC = 0.9 Hz, CAr), 145.6 (s, CAr), 147.9 (s, CAr), 175.1 (d,
JPC = 10.3 Hz, PCCN). 29Si{1H} NMR (59.63 MHz, CDCl3, 25
°C): δ −28.8 (d, JPSi = 1.4 Hz, SiAu), 13.1 (d, JPSi = 1.8 Hz, SiMe).
31P{1H} NMR (121.49 MHz, CDCl3, 25 °C): δ 45.5 (s). Minor
isomer (8%). 31P{1H} NMR (121.49 MHz, CDCl3, 25 °C): δ 40.8 (s).
Silacyclopropylidene-Pt0(dvtms) Complex (6). To a flask contain-
ing 1 (150 mg, 0.21 mmol) was added a platinum(0) 1,3-divinyl-
1,1,3,3-tetramethyldisiloxane complex in xylene (1.2 mL, 0.11 mmol)
at room temperature. After stirring for 2 h, all volatiles were removed
under vacuum, and the solid was washed with pentane to give the
analytically pure 6 as a white powder (152 mg, 70%). Crystals of
compound 6 suitable for X-ray diffraction analysis were obtained in a
dichloromethane/pentane solution at room temperature. Mp: 244−
Hz, PCSi), 52.6 (br s, CtBu), 52.9 (d, JPC = 1.1 Hz, CtBu), 90.1 (d, JPC
=
120.3 Hz, PCCN), 123.3 (s, CHAr), 124.3 (s, CHAr), 124.8 (s,
CHAr), 126.1 (s, 2 × CHAr), 126.6 (d, JPC = 3.0 Hz, CHAr), 127.8 (s,
CHAr), 128.3 (s, 2 × CHAr), 129.9 (s, 2 × CHAr), 132.5 (d, JPC = 5.0
Hz, CAr), 137.0 (d, JPC = 6.5 Hz, 2 × CHAr), 138.6 (s, CAr), 139.9 6(d,
JPC = 4.1 Hz, CAr), 148.2 (br s, 2 × CAr), 175.5 (d, JPC = 10.0 Hz,
PCCN), 184.5 (br, CO). 29Si{1H} NMR (59.63 MHz, THF-d8, 25
°C): δ −38.8 (d, JSiRh = 74.1 Hz, SiRh), 13.6 (s, SiMe). 31P{1H} NMR
(121.49 MHz, THF-d8, 25 °C): δ 46.6 (s). IR (KBr pellets): νCO
1984.4 (COtrans), 2070.2 (COcis) cm−1. Minor isomer (8%). 31P{1H}
NMR (121.49 MHz, THF-d8, 25 °C): δ 42.7 (s).
Silacyclopropylidene-CuICl Complex (4). To a flask containing 1
(40.0 mg, 0.057 mmol) and CuCl (5.6 mg, 0.057 mmol) was added
THF (1 mL) at RT. After stirring overnight at RT, all volatiles were
removed under vacuum, and the solid was washed with pentane, to
give the analytically pure 4 as a light-gray powder (45.0 mg, 98%).
Crystals of compound 4 suitable for X-ray diffraction analysis were
obtained by slow crystallization in a dichloromethane/diethyl ether
mixture at −30 °C. Mp: 158−159 °C. Major isomer (92%). 1H NMR
(300.18 MHz, CDCl3, 25 °C): δ 0.04 (s, 3H, CH3Si), 0.49 (s, 3H,
CH3Si), 0.95 (d, JHH = 6.7 Hz, 3H, CH3iPr), 1.15 (overlapped with
1
245 °C (dec). Major isomer (94%). H NMR (300.18 MHz, CDCl3,
CH3tBu, 6H, 2 × CH3iPr), 1.16 (s, 9H, 3 × CH3tBu), 1.25 (br d, JHH
=
1
1
25 °C): δ −0.65 (s, 3H, CH3Si), −0.43 (s, 3H, CH3Si), −0.23 (s, 3H,
CH3Si), 0.16 (s, 3H, CH3Si), 0.36 (s, 3H, CH3Si), 0.55 (s, 3H,
CH3Si), 0.86 (d, JHH = 6.6 Hz, 3H, CH3iPr), 0.97 (br s, overlapped with
CH3iPr, 1H, H2CCH) 0.99 (d, JHH = 6.6 Hz, 3H, CH3iPr), 1.10 (br s,
1H, 1/2H2CCH), 1.28 (d, JHH = 6.6 Hz, 3H, CH3iPr), 1.29 (d, JHH = 6.6
Hz, 3H, CH3iPr), 1.36 (br d, 1H, /2CH2Norb), 1.50 (overlapped with
CH3tBu, 1H, CH2CbridgeheadCP), 1.51 (s, 9H, 3 × CH3tBu), 1.53
7.7 Hz, 1H, /2CH2Norb), 1.34 (m, 1H, /2CH2CbridgeheadCP), 1.49 (s,
9H, 3 × CH3tBu), 1.60 (d, JHH = 6.7 Hz, 3H, CH3iPr), 1.61 (overlapped
with CH3iPr, 2H, 1/2CH2CbridgeheadCP 1/2CH2Norb), 1.74 (m, 2H,
,
CH2CbridgeheadCN), 2.47 (s, 1H, PCCHbridgehead), 2.97 (sep, JHH = 7.0
Hz, 1H, CHiPr), 3.20 (sep, JHH = 7.2 Hz, 1H, CHiPr), 3.24 (d, JPH
=
1
30.1 Hz, 1H, SiCH), 3.27 (s, 1H, NCCHbridgehead), 6.38 (m, 2H, HAr),
6.77 (m, 3H, HAr), 7.04−7.24 (6H, HAr), 7.55 (br, 2H, HAr). 13C{1H}
NMR (75.47 MHz, CDCl3, 25 °C): δ 3.5 (d, JPC = 2.2 Hz, CH3Si), 6.2
(br s, CH3Si), 23.4 (s, CH3iPr), 24.6 (s, CH3iPr), 24.6 (s,
CH2CbridgeheadCP), 26.2 (s, CH3iPr), 26.7 (s, CH3iPr), 27.9 (s,
CH2CbridgeheadCN), 27.9 (s, CHiPr), 28.5 (d, JPC = 1.9 Hz, SiCH),
1
(overlapped with CH3tBu, 1H, /2H2CCH), 1.56 (s, 9H, 3 × CH3tBu),
1.66 (br s, 1H, CH2CbridgeheadCP), 1.67 (br s, 1H, H2CCH), 1.74 (br d,
1H, 1/2CH2Norb), 1.84 (br d, 2H, CH2CbridgeheadCN), 2.59 (d, JHH = 13.5
Hz, 1H, 1/2H2CCH), 2.63 (s, 1H, PCCHbridgehead), 2.99 (d, JHH = 11.4
1
Hz, 1H, /2H2CCH), 3.06 (m, 1H, CHiPr), 3.34 (m, 1H, CHiPr), 3.38
28.7 (s, CHiPr), 32.4 (d, JPC = 4.8 Hz, 3C, 3 × CH3tBu), 33.4 (d, JPC
=
(d, JPH = 31.8 Hz, 1H, SiCH), 3.48 (s, 1H, NCCHbridgehead), 6.33 (m,
2H, HAr), 6.73 (m, 3H, HAr), 6.80−7.12 (6H, HAr), 7.51 (br, 2H,
HAr). 13C{1H} NMR (75.47 MHz, CDCl3, 25 °C): δ −1.8 (s, CH3Si),
4.5 Hz, 3C, 3 × CH3tBu), 44.0 (d, JPC = 8.7 Hz, NCCHbridgehead), 44.7
(d, JPC = 63.8 Hz, PCSi), 46.9 (d, JPC = 10.0 Hz, PCCHbridgehead), 47.2
(d, JPC = 8.2 Hz, CH2Norb), 52.4 (d, JPC = 1.5 Hz, CtBu), 52.8 (br s,
E
Inorg. Chem. XXXX, XXX, XXX−XXX