DEPROTONATION OF A CP-STAR METHYL-GROUP BY AN IRIDIUM ANILIDE - FORMATION, STRUCTURE, AND SOLUTION DYNAMICS OF AN ETA-4-TETRAMETHYLFULVENE COMPLEX

被引：60

作者：

GLUECK, DS ^{[1
]}

BERGMAN, RG ^{[1
]}

机构：

[1] UNIV CALIF BERKELEY,DEPT CHEM,BERKELEY,CA 94720

来源：

ORGANOMETALLICS | 1990年 / 9卷 / 11期

关键词：

D O I：

10.1021/om00161a006

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The new iridium amide complex Cp*IrPPh3-(Me)(NHPh) (1, Cp* = η5-C5Me5) reacts with 1,2-bis(diphenylphosphino)ethane (dppe) to give PPh3, aniline, and the tetramethylfulvene complex (η4-C5Me4CH2)Ir(dppe)Me (4), which has been characterized by X-ray crystallography and by variable-temperature NMR spectroscopy. Deprotonation of [Cp*Ir(dppe)Me]+I- (7) with KNHPh or KOBut also gives 4, suggesting that the anilide ligand is displaced from 1 as an anion, which immediately deprotonates a Cp* methyl group. The fact that deprotonation of 7-d3 (prepared from Cp*Ir(dppe) (6) and CD3I) gives 4-d3 demonstrates that the Cp* methyl is the kinetic site of deprotonation even though it is more remote than the Ir-bound methyl from the positively charged metal center. © 1990, American Chemical Society. All rights reserved.

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页码：2862 / 2863

页数：2

相关论文

共 17 条

[1] DI-U-OXO-(ETA-1-ETA-5-1,2,3,4-TETRAMETHYL-5-METHYLENE-1,3-CYCLOPENTADIENE-BIS[(ETA-PENTAMETHYLCYCLOPENTADIENYL)TITANIUM], (MU-O)2[MU-[ETA-1-ETA-5-C5(CH2)(CH3)4]][TI[ETA-5-C5(CH3)5]]2, A COMPLEX CONTAINING A BRIDGING TETRAMETHYLMETHYLENECYCLOPENTADIENYL LIGAND [J].

BOTTOMLEY, F ;

LIN, IJB ;

WHITE, PS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (03) :703-704

[2] A STRUCTURAL, KINETIC, AND THERMODYNAMIC STUDY OF THE REVERSIBLE THERMAL C-H ACTIVATION REDUCTIVE ELIMINATION OF ALKANES AT IRIDIUM [J].

BUCHANAN, JM ;

STRYKER, JM ;

BERGMAN, RG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (07) :1537-1550

[3] METAL ATOM SYNTHESIS AND PHOTOCHEMISTRY OF BIS(ETA-PENTAMETHYLCYCLOPENTADIENYL)-TUNGSTEN DIHYDRIDE [J].

CLOKE, FGN ;

GREEN, JC ;

GREEN, MLH ;

MORLEY, CP .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1985, (14) :945-946

[4] STRUCTURES OF CATIONIC DI-IRIDIUM COMPLEXES DERIVED FROM (ETA-5-C5ME5)IR(CO)2, INCLUDING THE DICATION [(ETA-5-C5ME5)(CO)2IR-IR(CO)2(ETA-5-C5ME5)]2+ AND THE BRIDGING METHYLENETETRAMETHYLCYCLOPENTADIENYL (TETRAMETHYLFULVENE) COMPLEX [(ETA-5-C5ME5)(CO)IR-IR(CO)2 (ETA-5-CH2C5ME4)]+ [J].

EINSTEIN, FWB ;

JONES, RH ;

ZHANG, XH ;

YAN, XQ ;

NAGELKERKE, R ;

SUTTON, D .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (19) :1424-1426

[5] CHIRAL PENTAISOPROPYL CYCLOPENTADIENYL AND PENTAISOPENTYL CYCLOPENTADIENYL COMPLEXES - ONE-POT SYNTHESIS BY FORMATION OF 10 CARBON CARBON BONDS FROM PENTAMETHYLCOBALTICINIUM [J].

GLOAGUEN, B ;

ASTRUC, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (11) :4607-4609

[6]

GLUECK DS, UNPUB

[7] PENTAMETHYLCYCLOPENTADIENYLRHODIUM AND -IRIDIUM HALIDES .I. SYNTHESIS AND PROPERTIES [J].

KANG, JW ;

MOSELEY, K ;

MAITLIS, PM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1969, 91 (22) :5970-&

[8] REACTIONS OF THE RU METHOXO COMPLEX .6. LIGAND-EXCHANGE DURING COMPLEXING DEPROTONATION TO AND MOLECULAR-STRUCTURE OF H4-1,5-CYCLOOCTADIENE)(H6-1,2,3,4-TETRAMETHYLFULVENE)RUTHENIUM [J].

KOLLE, U ;

KANG, BS ;

THEWALT, U .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1990, 386 (02) :267-273

[9] HIGH OXIDATION-STATE MONOPENTAMETHYLCYCLOPENTADIENYL TUNGSTEN METHYL COMPLEXES INCLUDING THE 1ST DO COMPLEX CONTAINING A HIGHLY DISTORTED METHYLENE LIGAND, W(ETA-5-C5ME5)(CH3)3(CH2) [J].

LIU, AH ;

MURRAY, RC ;

DEWAN, JC ;

SANTARSIERO, BD ;

SCHROCK, RR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (14) :4282-4291

[10] A KINETIC AND MECHANISTIC STUDY OF THE THERMOLYSIS OF BIS(PENTAMETHYLCYCLOPENTADIENYL)DIMETHYLTITANIUM(IV) [J].

MCDADE, C ;

GREEN, JC ;

BERCAW, JE .

ORGANOMETALLICS, 1982, 1 (12) :1629-1634