DIE KOORDINATIONSCHEMIE C=S-FUNKTIONELLER VERBINDUNGEN. VI. REAKTIONEN AN η1-, η2- UND η3-DITHIOESTER-KOMPLEXEN

Article abstract of DOI:10.1016/0022-328X(87)80247-4

The η¹-dithioester complexes W(CO)4(L) (η¹-S=C(Me)SMe) L = CO, P-i-Pr3) add PMe3 giving the betaines W(CO)4(L)(SC(Me)(SMe)PMe3).The uncoordinated dithioesters yield similar adducts S^-C(R)(SMe)P⁺Me3 (R = Me, Ph) which can be alkylated to the phosphonium salts I.Correspondingly, reaction with mer-W(CO)3(dmpe)(η²-S=C(Me)SMe) produces inter alia a metal-coordinated thioacylphosphonium ion.Coordinatively unsaturated metal fragments add to η³-dithioester complexes with formation of the binuclear compounds (CO)3(i-Pr3P)W(μ,η³-S=C(Me)SMe)W(CO)5 and (CO)3(Ph3P)Cr(μ,η³-S=C(Me)SMe)Cr(CO3)(dppe), respectively.With methyl iodide the η²-dithioester complexes yield the cations mer-2-MeSC(R)SMe)>⁺ (R = Me, Ph), whereas the η³ derivatives give the neutral compounds WI(CO)3(PR3)(η²-MeSC(Me)SMe) (R = i-Pr, Cy, Ph).The η³-dithiocarbenium complex WI(CO)3(η³-C(Me)(SMe)2) which is formed as a side product for R = Ph was characterized by X-ray crystallography.