The reaction of [{W(CO)(5)}(2)PCl] with K[Co(CO)(4)] yields the novel compounds [{W(CO)(4)CO2(CO)(6)}{mu(3)-PW(CO)(5)}(2)] (3) and [{(CO)(4)WCO3(CO)(6)}{mu(3)-PW(CO)(5)}(3)] (4) along with known derivatives [CO2(CO)(6){mu,eta(2)-PW(CO)(5)}(2)] (1) and [CO3(CO)(9){mu(3)-PW(CO)(5)}] (2). The complex [{W-2(CO)(8)(mu-CO)}{mu,eta(2):eta(1):eta(1)-PW(CO)(5)}(2))] (5) was synthesised by treating Na-2[W-2(CO)(10)] with PBr3. Reaction of K[Mn(CO)(5)] with SbCl3 affords [Sb{Mn(CO)(5)}(3)] (6) in high yields. The spectroscopic and structural characterisation of the novel products is discussed, as well as the thermolytic behaviour of 2, 3 and 6 for the potential formation of novel phases of transition metal pnictides. (C) Wiley-VCH Verlag GmbH Co.