Activations of silanes with [PhB(CH2PPh2)3]Ir(H)(η3-C8H13).: Formation of iridium silylene complexes via the extrusion of silylenes from secondary silanes R2SiH2

被引：95

作者：

Feldman, JD ^{[1
]}

Peters, JC ^{[1
]}

Tilley, TD ^{[1
]}

机构：

[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

来源：

ORGANOMETALLICS | 2002年 / 21卷 / 20期

关键词：

D O I：

10.1021/om020389u

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The abstraction of methide from (Me3P)(3)Ir(SiHMes(2))(Me)(H) (1) with B(C6F5)(3) gave the silylene complex [fac-(Me3P)(3)(H)(2)Ir(SiMes(2))] [MeB(C6F5)(3)] (2) via 1,2-hydrogen migration. Secondary silanes (H2SiR2) reacted with [PhBP3]Ir(H)(eta(3)-C8H13) (3) (where [PhBP3] = PhB(CH2PPh2)(3)(-)) to give silylene complexes of the type [PhBP3](H)(2)Ir=SiR2 (R = 2,4,6-trimethylphenyl (Mes), 4a; R = Ph, 4b; R = Et, 4c; R = Me, 4d), with loss of cyclooctene. Analogously, the germylene complex [PhBP3](H)(2)Ir=GeMes(2) was obtained via the reaction of 3 with Mes(2)GeH(2). Primary silanes (H3SiR) reacted with 3 to give [PhBP3](H)(2)Ir=Si(R)(c-C8H15) (R = Mes, 8a; R = 2,4,6-triisopropylphenyl (Trip), 8b) via an intermediate silylene complex with an Si-H bond, [PhBP3](H)(2)Ir=Si(R)(H). With tertiary silanes (R3SiH), silyl-capped trihydride complexes of the type [PhBP3]IrH3(SiR3) (R = Et, 7a; R = Me, 7b) and 1,3-cyclooctadiene were produced. The mechanisms of these processes are discussed.

引用

页码：4065 / 4075

页数：11

共 69 条

[1] Formation of hydrido-eta(3)-allyl complexes of Ir-III by sequential olefinic C-H bond activation and C-C coupling of alkenyl and olefin ligands [J].

Alvarado, Y ;

Boutry, O ;

Gutierrez, E ;

Monge, A ;

Nicasio, MC ;

Poveda, ML ;

Perez, PJ ;

Ruiz, C ;

Bianchini, C ;

Carmona, E .

CHEMISTRY-A EUROPEAN JOURNAL, 1997, 3 (06) :860-873

[2] A stable silylene in a reactive environment:: Synthesis, reactivity, and silicon extrusion chemistry of a coordinatively unsaturated ruthenium silylene complex containing chloride and η3-P-C-P ligands [J].

Amoroso, D ;

Haaf, M ;

Yap, GPA ;

West, R ;

Fogg, DE .

ORGANOMETALLICS, 2002, 21 (03) :534-540

[3]

[Anonymous], COMMENTS INORG CHEM, DOI 10.1080/02603599008048649

[4] CARBONYLDIHYDRIDO(TRIMETHYLGERMYL)BIS(TRIPHENYLPHOSPHINE)IRIDIUM(III) HEMIBENZENE SOLVATE, (C40H41GEIROP2.C6H6)-C-1/2 [J].

BELL, NA ;

GLOCKLING, F ;

SCHNEIDER, ML ;

SHEARER, HMM ;

WILBEY, MD .

ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1984, 40 (APR) :625-628

[5] SYNTHESIS AND CHARACTERIZATION OF STERICALLY HINDERED DIARYLSILANES CONTAINING 2,4,6-TRIMETHYLPHENYL AND 2,4,6-TRIS(TRIFLUOROMETHYL)PHENYL SUBSTITUENTS, X-RAY CRYSTAL-STRUCTURE OF BIS[2,4,6-TRIS(TRIFLUOROMETHYLPHENYL)]FLUOROSILANE [J].

BRADDOCKWILKING, J ;

SCHIESER, M ;

BRAMMER, L ;

HUHMANN, J ;

SHALTOUT, R .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1995, 499 (1-2) :89-98

[6]

*BRUK INC, 1995, SAINT SAX AR DET INT

[7] Reactions of the stable bis(amino)silylene Si[{N(CH2tBu)}2C6H4-1,2] with group 3 or lanthanide metal organic compounds.: Crystal structures of [Ln(η5-C5H5)3Si{[N(CH2tBu)]2C6H4-1,2}]•C7H8 (Ln = Y or Yb) [J].

Cai, XP ;

Gehrhus, B ;

Hitchcock, PB ;

Lappert, MF .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 2000, 78 (11) :1484-1490

[8] Factors governing the equilibrium between metal-alkyl, alkylidene and alkylidyne:: MCX2R, X-M=CXR and X2MCR [J].

Caulton, KG .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2001, 617 (01) :56-64

[9]

Coalter JN, 2000, NEW J CHEM, V24, P835

[10] Carbene transposition involving double dehydrogenation of an sp3 carbon [J].

Coalter, JN ;

Huffman, JC ;

Caulton, KG .

CHEMICAL COMMUNICATIONS, 2001, (13) :1158-1159

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