Die koordinationscheme CS-funktioneller verbindungen: VI. Reactionen an η 1-, η 2- und η 3-dithioester-komplexen

Abstract

The η 1-dithioester complexes W(CO) 4(L) (η 1-SC(Me)SMe) (L  CO, P-i-Pr 3) add PMe 3 giving the betaines W(CO) 4(L)(SC(Me)(SMe)(PMe 3). The uncoordinated dithioesters yield similar adducts − C(R)(SMe) P + Me 3 (R  Me, Ph) which can be alkylated to the phosphonium salts [RC(SMe) 2PMe 3]I. Correspondingly, reaction with mer-W(CO) 3)dmpe)(η 2-SC(Me)SMe) produces inter alia a metal-coordinated thioacylphosphonium ion. Coordinately unsaturated metal fragments add to η 3-dithioester complexes with formation of the binuclear compounds (CO) 3(i-Pr 3P)W(μ,η 3-SC(Me)SMe)W(CO) 5 and (CO) 3(Ph 3P)Cr(μ,η 3-SC(Me)SMe)Cr-(CO) 3(dppe), respectively. With methyl iodide the η 2-dithioester complexes yield the cations mer-[W(CO) 3(dppe)(η 2-MeSC(R)SMe)] + (R  Me, Ph), whereas the η 3 derivatives give the neutral compounds WI(CO) 3(PR 3)(η 2-MeSC(Me)SMe) (R  i-Pr, Cy, Ph). The η 3-dithiocarbenium complex WI(CO) 3(η 3-C(Me)(SMe) 2) which is formed as a side product for R  Ph was characterized by X-ray crystallography.