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Titolo:
Synthesis and property of phosphenium complexes containing double bond character between a transition metal and a phosphorus atom
Autore:
Nakazawa, H; 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 SYNTHETIC ORGANIC CHEMISTRY JAPAN
fascicolo: 1, volume: 59, anno: 2001,
pagine: 52 - 61
SICI:
0037-9980(200101)59:1<52:SAPOPC>2.0.ZU;2-N
Fonte:
ISI
Lingua:
JPN
Soggetto:
GROUP-14 ELEMENT LIGAND; X-RAY CRYSTAL; MOLYBDENUM COMPLEXES; MOLECULAR-STRUCTURES; MIGRATORY INSERTION; BORON TRIHALIDES; VINYL CATIONS; REACTIVITY; CHEMISTRY; PHOSPHITE;
Keywords:
phosphenium complex; M-P double bond; theoretical calculation; OR abstraction; migratory insertion; 1,3-migration; rotational barrier;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
73
Recensione:
Indirizzi per estratti:
Indirizzo: Nakazawa, H Hiroshima Univ, Grad Sch Sci, Dept Chem, 1-3-1 Kagamiyama, Higashihiroshima 7398526, Japan Hiroshima Univ 1-3-1 Kagamiyama Higashihiroshima Japan 7398526
Citazione:
H. Nakazawa e K. Miyoshi, "Synthesis and property of phosphenium complexes containing double bond character between a transition metal and a phosphorus atom", J SYN ORG J, 59(1), 2001, pp. 52-61

Abstract

In this review, a new and general method for the preparation of phosphenium complexes of transition metals has been reported. The stability of phosphenium complexes increases with going to a heavier congener among group 6 transition metals, and with increasing the number of amino substituents on the phosphenium phosphorus. The X-ray structures, P-31 NMR and Mo-95 NMR studies, and theoretical calculations have revealed that pi back donation from a filled d orbital of a transition metal to an empty p orbital of a phosphenium phosphorus is a dominant contribution. Unique reactivities of phosphenium complexes have been developed: (i) heteroatom migration from a tertiaryphosphorus to a phosphenium phosphorus in a coordination sphere, (ii) migratory insertion of a phosphenium ligand into a carbon-transition metal bond, (iii) 1,3-migration of an alkyl group from a stannyl ligand to a phosphenium phosphorus. Activation parameters concerning phosphenium ligand rotation along the P-M axis have been estimated.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 02/04/20 alle ore 09:10:28