Selective Cα–Cβ bond cleavage by water in allenylidene and alkenylvinylidene ruthenium complexes

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Claudio Bianchini, Maurizio Peruzzini, Fabrizio Zanobini, Carlos Lopez, Isaac de los Rios and Antonio Romerosa


Abstract

The Ru(II) complex mer,trans-[(PNP)RuCl2(PPh3)] [PNP = MeCH2CH2N(CH2CH2PPh2)2] reacts in refluxing THF with propargyl alcohols HC[triple bond, length half m-dash]CCRR′OH (R = R′ = Me, Ph; R = Me, R′ = Ph) yielding either the allenylidene complex fac,cis-[(PNP)RuCl2{C[double bond, length half m-dash]C[double bond, length half m-dash]CPh2}] or the alkenylvinylidene derivatives fac,cis-[(PNP)RuCl2{C[double bond, length half m-dash]C(H)C(R)[double bond, length half m-dash]CH2}] (R = Me, Ph); treatment of all these complexes in CH2Cl2 or THF with water results in the formation of the ruthenium carbonyl fac,cis-[(PNP)RuCl2(CO)] and free alkenes H2C[double bond, length half m-dash]CRR′ (R = R′ = Me, Ph; R = Me, R′ = Ph) via regioselective Cα–Cβ bond cleavage.


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