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Titolo:
Conversion of a stannyl-phosphenium complex into a stannylene-phosphine complex of Mo and W: double bond migration from M=P to M=Sn
Autore:
Nakazawa, H; Kishishita, M; Ishiyama, T; Mizuta, T; Miyoshi, K;
Indirizzi:
Hiroshima Univ, Grad Sch Sci, Dept Chem, Higashihiroshima 7398526, Japan Hiroshima Univ Higashihiroshima Japan 7398526 hihiroshima 7398526, Japan
Titolo Testata:
JOURNAL OF ORGANOMETALLIC CHEMISTRY
fascicolo: 1, volume: 617, anno: 2001,
pagine: 453 - 463
SICI:
0022-328X(20010115)617:1<453:COASCI>2.0.ZU;2-E
Fonte:
ISI
Lingua:
ENG
Soggetto:
TRANSITION-METAL COMPLEXES; GROUP-14 ELEMENT LIGAND; MOLYBDENUM COMPLEXES; BORON TRIHALIDES; LEWIS-ACID; PHOSPHORUS; REACTIVITY; CHEMISTRY; ALKYL; ISOMERIZATION;
Keywords:
phosphenium complex; stannylene complex; migration; double bond;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
41
Recensione:
Indirizzi per estratti:
Indirizzo: Nakazawa, H Hiroshima Univ, Grad Sch Sci, Dept Chem, Higashihiroshima 7398526, Japan Hiroshima Univ Higashihiroshima Japan 7398526 7398526, Japan
Citazione:
H. Nakazawa et al., "Conversion of a stannyl-phosphenium complex into a stannylene-phosphine complex of Mo and W: double bond migration from M=P to M=Sn", J ORGMET CH, 617(1), 2001, pp. 453-463

Abstract

Four-legged piano-stool complexes, Cp(CO)(2)(SnR3)M{PN(Me)CH2CH2NMe(OMe)},containing a stannyl group (SnPh3, SnMe3, (SnBu3)-Bu-n) and diamino-substituted phosphite (PN(Me)CH2CH2NMe(OMe) which is abbreviated as PNN(OMe)) were prepared for Mo and W, and the reactions of these complexes with a Lewis acid (BF3. OEt2 and TMSOTf) were examined. For the SnPh3 and SnMe3 complexes, stannylene complexes [Cp(CO)(2)(SnR2)M{PNN(R)}]X (X = OTf- or BF4-) wereformed with migration of an R group from Sn to P. X-ray analyses of [Cp(CO)(2)(SnPh2)W{PNN(Ph)}]OTf and [Cp(CO)(2)(SnMe2)-W{PNN(Me)}]OTf reveal that these complexes are regarded as stannylene tungsten complexes stabilized byan oxygen of OTf. In the reaction of the (SnBu3)-Bu-n complex with TMSOTf,the corresponding stannylene complex and an unexpected neutral phospheniumcomplex, Cp(CO)(2)M{PNN}, were formed. However, when BF2. OEt2 was used inplace of TMSOTf, cationic phosphenium complexes in addition to a neutral phosphenium complex were observed. In any case, an OMe anion abstraction by a Lewis acid takes place at the first stage to give a cationic phosphenium complex, and then aryl or alkyl migration takes place to give a stannylene complex. A relatively strong Sn-Bu-n bond retards the alkyl migration, resulting in the observation of the cationic phosphenium complexes. (C) 2001 Elsevier Science B.V. All rights reserved.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 05/04/20 alle ore 22:52:06