A NOVEL SYNTHETIC APPROACH TO HIGHLY REACTIVE INTERMEDIATES CONTAINING A METAL-PHOSPHORUS TRIPLE BOND

Citation
M. Scheer et al., A NOVEL SYNTHETIC APPROACH TO HIGHLY REACTIVE INTERMEDIATES CONTAINING A METAL-PHOSPHORUS TRIPLE BOND, Chemistry (Weinheim), 4(10), 1998, pp. 1917-1923
Citations number
27
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Chemistry
Journal title
ISSN journal
0947-6539
Volume
4
Issue
10
Year of publication
1998
Pages
1917 - 1923
Database
ISI
SICI code
0947-6539(1998)4:10<1917:ANSATH>2.0.ZU;2-S
Abstract
Thermolysis of [CpP{W(CO)(5)}(2)] (la) induces a Cp* migration from a sigma-bound state at the phosphorus atom to eta(5) coordination at th e transition metal. Thereby the unsaturated P atom undergoes an unusua l C-H activation to yield the novel complex [(CO)(3)W(eta(5)-C5Me4CH2) P(H) --> W(CO)(5)] (2). Additionally, a highly reactive intermediate o f the type [Cp(CO)(2) W=P --> W(CO)(5)], containing a tungsten-phosph orus tripie bond, is formed. The dimerisation of this sterically unpro tected intermediate leads to [Cp-2(CO)(4)W-2(mu, eta(2)-P-2{W(CO)(5)} ] (3), Furthermore. the tetranuclear cluster [{W(CO)(3)CpW}(2)(mu(3)- P)(2){mu 3-PW(CO)(5)}(2)] (4) was isolated. The existence of a phosphi do-ligand intermediate finds further support by a trapping reaction in the presence of tBuC=P. Here, the thermolysis of la leads to the form ation of the novel complex [Cp(CO)(2)W{eta(3)-(PPC(O)CtBu)W(CO)(5)}] (5), containing a diphosphacyclobutenone ligand. Comprehensive structu ral and spectroscopic data are given for the products.