Journal of Organometallic Chemistry p. 287 - 303 (1987)
Update date:2022-07-30
Topics:
Schenk, Wolfdieter A.
Rueb, Doris
Burschka, Christian
Esters of dithiocarboxylic acids SC(R)SMe (R Me, Ph) coordinate to mononuclear transition metal fragments in three different ways. η1(S)-coordination of the CS group is found in cases of low electron density at the metal, e.g. M(CO)5 (η1-SC(Me)SMe) (M Cr, W) and cis-W(CO)4(PR3)(η1-SC(Me)SMe) (PR3 P-i-Pr3, PPhMe2). The more electron-rich tricabonyl complexes occur in two isomeric forms, fac-W(CO)3(R2PC2H4-PR2)(η1-SC(R)SMe) and mer-W(CO)3(R2PC2H4-PR2) (η2-SC(R)(SMe) (R Me, Ph) with the η2-dithioester acting as a good π-acceptor ligand. In the compounds fac-M(CO)3(PR)3(η3-SC(Me)SMe) (M Cr, Mo, W) and cis-Mo(CO)2(dppe)(η3-SC(Me)SMe) the dithioester functions as a four-electron ligand with the SMe group also being coordinated to the metal. The three different bonding modes are readily distinguished by 13C NMR spectroscopy A X-ray structure analysis of fac-W(CO)3(P-i-Pr3)(η3-SC(Me)SMe) reveals the allylic-type coordination of the dithioester ligand.
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