Iodo-alkynyl- and iodo-butadiynyl-ruthenium complexes

Addition of [I(py)2]BF4 to Ru(Ctriple bond; length of mdashCH)(dppe)Cp∗ gave the iodovinylidene [Ru(double bond; length as m-dashCdouble bond; length as m-dashCHI)(dppe)Cp∗]BF41, which could be deprotonated to Ru(Ctriple bond; length of mdashCI)(dppe)Cp∗ 2. The attempted preparation of Ru(Ctriple bond; length of mdashCCtriple bond; length of mdashCI)(dppe)Cp∗, followed by derivatisation with tcne, gave the dienynyl Ru{Ctriple bond; length of mdashCC[double bond; length as m-dashC(CN)2]CIdouble bond; length as m-dashC(CN)2}(dppe)Cp∗ 3. The Pd(0)/Cu(I)-catalysed reaction of 3 with Ru{Ctriple bond; length of mdashCCtriple bond; length of mdashCAu(PPh3)}(dppe)Cp∗ afforded Ru{Ctriple bond; length of mdashCCdouble bond; length as m-dashC(CN)2Cdouble bond; length as m-dashC(CN)2Au(PPh3)}(dppe)Cp∗ 4 by formal replacement of I+ by [Au(PPh3)]+. XRD structures of 1–4 are reported.