P-H FUNCTIONAL ZIRCONOCENE PHOSPHIDO COMP LEXES - SYNTHESIS AND MOLECULAR-STRUCTURE OF CIS-[CP'2ZR(MU-PHR)](2) (CP'=C(5)H(4)ME, R=C4H9 ((T)BU), C10H15 (AD))

The phosphido-bridged dinuclear zirconocene(III) complexes cis-[Cp'Zr- 2(mu-PHR)](2) (Cp' = C(5)H(4)Me, R = (t)Bu (1), Ad (2)) are isolated f rom the reaction of Cp'2ZrCl2 with solvent-free LiPHR (R = C4H9((t)Bu) , C10H15 (Ad)). It can be shown by P-31 NMR spectroscopy that the comp lexes Cp'Zr-2(PHR)(2) and Cp'Zr-2(PR-PR-PR) are also formed, as well a s the oxidation products of LiPHR, meso- and D,L-P(2)H(2)R(2) 1 and 2 were characterized spectroscopically (NMR, IR, MS) and by X-ray struct ure determination. Only one isomer (cis) is present in the solid state and in solution. The Zr-P bond lengths range from 2.6161(8) Angstrom to 2.6452(8) Angstrom in 1, and from 2.6512(10) Angstrom to 2.6714(12) Angstrom in 2. The central Zr P-2 ring of 1 and 2 is slightly puckere d (dihedral angle: 15.32 degrees (1), 17.42 degrees (2)). The long Zr. ..Zr distance of 3.76 Angstrom (1) and 3.81 Angstrom (2) indicates the absence of Zr-Zr interaction.