Catalytic and stoichiometric reactions of tertiary silanes with [Ir(Me)2CpL] (Cp = η5-C5Me5; L = PMe3, PMe2Ph, PMePh2, PPh3) in the presence of one-electron oxidants.: A unique case of Si-H, Si-C, Ir-C and P-F bonds one-step activation:: crystal structure of [Ir(Ph)(SiPh2F)Cp*(PMe3)]

被引：17

作者：

Diversi, P

Marchetti, F

Ermini, V

Matteoni, S

机构：

[1] Univ Pisa, Dipartimento Chim & Chim Ind, I-56126 Pisa, Italy

[2] Univ La Sapienza, Dipartimento Ingn Chim Mat & Mat Prime & Met, I-00195 Rome, Italy

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2000年 / 593卷

关键词：

iridium; electron-transfer catalysis; silanes; dehydrocoupling;

D O I：

10.1016/S0022-328X(99)00469-6

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The iridium(III) dimethyl derivatives [Ir(Me)(2)Cp*L] (Cp* = eta(5)-C5Me5; L = PMe3 1a, PPh3 1d) catalyze the dehydrogenative coupling of dimethylphenylsilane in the presence of one-electron oxidants to yield Me2PhSiSiPhMe2. Compounds 1a-d react with triphenylsilane in the presence of [FeCp2]PF6 to give methane and [Ir(Ph)(SiFPh2)Cp*L] (L = PMe3 (2a), PMe2Ph (2b), PMePh2 (2c), PPh3 (2d)). 2a was structurally characterized by single-crystal X-ray diffraction experiments. The 'three-legged piano stool' coordination polyhedron is slightly deformed. (C) 2000 Elsevier Science S.A. All rights reserved.

引用

页码：154 / 160

页数：7

共 38 条

[1] CYCLOMETALLATION REACTIONS IN NEOPENTYL AND TRIMETHYLSILYLMETHYL SYSTEMS OF RHODIUM(III) AND IRIDIUM(III) - FORMATION AND X-RAY CRYSTAL-STRUCTURES OF THE 4-MEMBERED METALLACYCLES "[RH(CH2CME2CH2)(ETA-5-C5ME5)(PPH3)] AND [IR(CH2SIME2CH2)(ETA-5-C5ME5)(PPH3)]
ANDREUCCI, L
DIVERSI, P
INGROSSO, G
LUCHERINI, A
MARCHETTI, F
ADOVASIO, V
NARDELLI, M
[J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1986, (03): : 477 - 487
[2] NEOPENTYL AND TRIMETHYLSILYLMETHYL COMPOUNDS OF RHODIUM(III) AND IRIDIUM(III) WITH ORTHO-METALATED TRIPHENYLPHOSPHINE - X-RAY CRYSTAL-STRUCTURE OF [IR(C6H4PPH2)(CH2SIME3)(ETA-5-C5ME5)]
ANDREUCCI, L
DIVERSI, P
INGROSSO, G
LUCHERINI, A
MARCHETTI, F
ADOVASIO, V
NARDELLI, M
[J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1986, (04): : 803 - 812
[3] [Anonymous], COMMENTS INORG CHEM, DOI 10.1080/02603599008048649
[4] (Phosphinoalkyl)silyl complexes .11. Structural influence of the chelate dimethyl((diphenylphosphino)ethyl)silyl group. Irregular 5-coordinate geometry at a d(6) center. X-ray crystal and molecular structures of three silyliridium(III) complexes [Ir(chel)(2)Cl, IrH(chel)(PPh(3))(CO)Cl, IrH(chel)(cod)Cl; Chel=PPh(2)CH(2)CH(2)SiMe(2)-, cod=cycloocta-1,5-diene]
Auburn, MJ
HolmesSmith, RD
Stobart, SR
Bakshi, PK
Cameron, TS
[J]. ORGANOMETALLICS, 1996, 15 (13) : 3032 - 3036
[5] FORMATION OF SI-SI BONDS FROM SI-H BONDS IN THE PRESENCE OF HYDROSILATION CATALYSTS
BROWNWENSLEY, KA
[J]. ORGANOMETALLICS, 1987, 6 (07) : 1590 - 1591
[6] FACILE INTERMOLECULAR ACTIVATION OF C-H BONDS IN METHANE AND OTHER HYDROCARBONS AND SI-H BONDS IN SILANES WITH THE IR(III) COMPLEX CP-ASTERISK-(PME3)IR(CH3)(OTF)
BURGER, P
BERGMAN, RG
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (22) : 10462 - 10463
[7] A STABLE ETA-2-SILENE COMPLEX OF IRIDIUM - (ETA-5-C5ME5)(PME3)IR(ETA-2-CH2=SIPH2)
CAMPION, BK
HEYN, RH
TILLEY, TD
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (10) : 4079 - 4081
[8] PHENYL TRANSFER FROM SILICON TO PLATINUM VIA THE ORTHO METALATION OF A PHENYLSILYL LIGAND
CHANG, LS
JOHNSON, MP
FINK, MJ
[J]. ORGANOMETALLICS, 1991, 10 (05) : 1219 - 1221
[9] DEHYDROGENATIVE COUPLING OF DIARYLSILANES
CHANG, LS
COREY, JY
[J]. ORGANOMETALLICS, 1989, 8 (08) : 1885 - 1893
[10] Reactions of hydrosilanes with transition-metal complexes: Formation of stable transition-metal silyl compounds
Corey, JY
Braddock-Wilking, J
[J]. CHEMICAL REVIEWS, 1999, 99 (01) : 175 - 292

← 1 2 3 4 →

Catalytic and stoichiometric reactions of tertiary silanes with [Ir(Me)2Cp*L] (Cp* = η5-C5Me5; L = PMe3, PMe2Ph, PMePh2, PPh3) in the presence of one-electron oxidants.: A unique case of Si-H, Si-C, Ir-C and P-F bonds one-step activation:: crystal structure of [Ir(Ph)(SiPh2F)Cp*(PMe3)]

Catalytic and stoichiometric reactions of tertiary silanes with [Ir(Me)2CpL] (Cp = η5-C5Me5; L = PMe3, PMe2Ph, PMePh2, PPh3) in the presence of one-electron oxidants.: A unique case of Si-H, Si-C, Ir-C and P-F bonds one-step activation:: crystal structure of [Ir(Ph)(SiPh2F)Cp*(PMe3)]