Complexes with a metal-phosphorus triple bond as versatile building blocks in coordination and organometallic chemistry

Trapping reactions of the phosphido complex intermediate [Cp*(CO)(2)Wequivalent toP-->W(CO)(5)], generated by thermolysis of [Cp*P{W(CO)(5)}(2)] 1, occur via [2+2] cycloaddition reactions with P-4, phosphaalkynes, alkynes, and [CpMo(CO)(2)](2), respectively. However, with nitriles, insertion reactions into the P-C sigma bond of 1 are observed already at room temperature to give novel P-containing heterocycles. Furthermore, irradiation of 1 gives the tetrahedral complex [Cp*(CO)(6)W-2}(mu-H)(mu, eta(2)-P-2){W(CO)(5)}(2)], which indicates that besides the formation of the triple-bond intermediate [Cp*(CO)(2)Wequivalent toP-->W(CO)(5)] a second Cp* elimination intermediate of the type [P{W(CO)(5)}(2)] occurs.