Synthesis and spectroscopic characterisation of some pentacarbonyltungsten(0) complexes with mono- and bicyclic phosphirane ligands: Crystal structure of [{(Me3Si)(2)HCPC(H)H-C(H)Ph}W(CO)(5)]

The tungsten(0) complex [{(Me3Si)(2-) HCPC(Ph) = N}W(CO)(5)] (1) reacts upo n heating with alkene derivatives 2, 6, 8, and 10 in toluene to form benzon itrile and the complexes [{(Me3si),HCPC(R-1,R-2)-C(R-3,R-4}W(CO)(5)] (4, 7a ,b, 9a,b, 11a,b) (4 (trans): R-1,R-3 = Ph, R-2, R-4 = H, 7a,b (cis, meso an d rac): R-1,R-3 = Ph, R-2,R-4 = H, 9a, b (RR und SS): R-1 = Ph, R-2,R-3,R-4 = H, 11a,b: R-1 = R-3 = (CH2)(4), R-2,R-4 = H). Spectroscopic and mass spe ctrometric data are discussed. The structure of the complex 9 a was determi ned by X-ray single crystal structure analysis showing characteristic data for the phosphirane ring such as a narrow angle at phosphorus (49,2(2)degre es), different P-C distances (P-C(6) 182,1(5) and P-C(7) 185,2(4)pm) and 15 2,9(6)pm for the basal C-C bond.