COORDINATION CHEMISTRY AND LIGAND PROPERTIES OF CHLOROMETHYLCHLOROPHOSPHINES R(CL)P-CH2-CL - MOLECULAR-STRUCTURE OF TRANS-CL2PD[TBU(CL)P-CH2-CL](2)

Reaction of the chloromethylchlorophosphines R(Cl)P-CH2-Cl (R = Cl, tB u, C6H11, NEt2, NPh2) (L) with C7H8Mo(CO)(4) or (CO)(5)W(Py), (CO)(6)W and (CO)(5)W(THF) yields the complexes cis-Mo(CO)(4)L-2(2a - 2e) or ( CO)(5)WL (3a - 3c), respectively, in high yields. The palladium(II) co mplexes PdCl2L2 (4a - 4c) are obtained on treatment of 1a, 1b and 1e w ith 1,5-cyclooctadiene palladium(II) chloride or anhydrous palladium(I I) chloride in a homogeneous or heterogeneous reaction, respectively. 4a - 4c are formed as a mixture of cis- and trans-isomers. The C-13{H- 1} NMR and H-1 NMR spectra of 2a - 4c have been analysed, the trans-st ructure of 4c could be assigned to the predominant isomer. The X-ray s tructural analysis of Je (triclinic, space group P (1) over bar) revea ls a trans-square planar coordination at palladium with an antiperipla nar arrangement of the bulky tBu substituents at the phosphorus atoms. Electronic (Sigma x(i)(Mo)) and steric ligand parameters (theta) are given for the chloromethylchlorophosphines R(Cl)P-CH2-Cl (R = Cl, tBu, C6H11,NEt2, NPh2).