Methylthiocarbyne complexes

The methoxycarbyne complex Tp W( = COMe)(CO)2 also reacts at the carbyne substituent with nucleophiles attacking the methoxide Me group, delivering Me and generating [Tp W(CO)3] via an Sn2 reaction.The reactivity of the methoxycarbyne complex Tp W( = COMe)(CO)2 thus differs considerably from that of the methylthiocarbyne complex Tp W( = CSMe)(CO)2, which reacts with phosphines at the carbyne carbon to undergo nucleophilic displacement of the methylthiolate substituent to produce phosphoniocarbyne complexes.The... 

Angelici has demonstrated that protonation of the methylthiocarbyne complex HBpz3(CO)2W =CSMe affords the cationic Fischer-type rj -thiocarbene complex [HBpz3(C0)2W-Ti -(=C(H)SMe)][CF3S03] [421. However, the comparable cyclopentadienyl substituted rj -thiocarbene complexes [Cp(CO)2M-r 2-(=C(R)SMe)][BF4] still contain a nucleophilic carbene carbon whereas an amphiphilic behavior is found for the trimethylphosphine-sub-stituted derivatives Thus, nucleophiles as well as electrophiles add to the carbene carbon of [Cp(CO)(PMe3)M-Ti2-(=C(R)SMe)][BF4] [41]. 

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