Abstract
A variety of alkyne, alkynyl, alkylidyne and alkylidene complexes has been obtained from the alkynes RCCH (R = Ph, CO2Me or CO2Et). The reactions of these alkynes with trans-[M(N2)2(dppe)2](M = Mo or W, dppe = Ph2PCH2CH2PPh2) and trans-[Mo(N2)2(depe)2](depe = Et2PCH2CH2PEt2) give the alkyne complex [Mo(HCCPh)2(dppe)2]A, the alkynyl complexes [MH2(CCR)2(L–L)2]B(M = Mo or W; R = Ph, CO2Me or CO2Et; L–L = dppe; M = Mo, R = Ph, L–L = depe) and trans-[M(CCR)2(dppe)2]C(M = Mo or W; R = Ph, CO2Me or CO2Et) depending on the conditions. The redox properties and interconversion of B and C are described and the X-ray crystal structures of B(M = W, R = CO2Me, L–L = dppe) and C(M = Mo, R = Ph) are presented. The complexes [WH2(CCR)2(dppe)2]B(R = CO2Me or Ph) react with HBF4 to give [WF(CCH2CO2Me)(dppe)2]D and [WF(CHCH2Ph)(dppe)2]BF4E respectively. The polymerisation of RCCH (R = H or Ph) at these metal centres is also discussed.
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