The course of electrophilic addition to the ruthenium(II) chloro vinylidenes [Cp*Cl(PPh 3 )Ru(CCHR)] is influenced by the steric properties of the electrophile and ruthenium complex. Thus, H + selectively adds to C β of the vinylidene ligand to yield the ruthenium(IV) carbynes [Cp*Cl(PPh 3 )Ru(CCH 2 R)][A] (A = BF 4 -, BAr f 4 - ), while the comparably larger Me + (from MeOTf) abstracts Cl - to yield, after anion coordination, [Cp*(OTf)(PPh 3 )Ru(CCHR)] and MeCl.
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Beach et al. (2003) studied this question.
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