Synthesis and reactivity of substituted cyclopentadienyl diphenylphosphido complexes of zirconium(IV). X-Ray crystal structure of [(C5H4SiMe3)2Zr(PPh2)2]

The syntheses of [(C5H4SiMe3)2Zr(PPh2)2] (1) and [(C5H5)(C5Me5)Zr(PPh2)2] (2) are described. The X-ray crystal structure of 1 has been determined (monoclinic, P21/n; a = 17.951(8); b = 23.776(11); c = 9.163(10) Å; β = 99.29(6)°; Z = 4) and it contains two distinct types of phosphido-ligands. Cyclic voltammetry measurements and chemical reduction of 1 are described, and the monophosphido ZrIII adduct species, [(C5H4SiMe3)2Zr(PPh2) (PhCCH)] identified by electron spin resonance spectroscopy. Reaction of 1 with the rhodium complex [Rh2(μ-S-tBu)2 (CO)4] affords the heterometallic complex [{C5H4SiMe3)2Zr(μ-PPh2)2(Rh(μ-S-tBu)2Rh}(μ-PPh2) 2Zr(C5H4SiMe3)2] (13). The catalysis of the hydroformylation of 1-hexene with 3 as catalyst has been investigated. \ud \ud Synthesis and reactivity of substituted cyclopentadienyl diphenylphosphido complexes of zirconium(IV). X-ray crystal structure of [(C5H4SiMe 3)2Zr(PPh2)2] (PDF Download Available). Available from: http://www.researchgate.net/publication/222459293_Synthesis_and_reactivity_of_substituted_cyclopentadienyl_diphenylphosphido_complexes_of_zirconium(IV)._X-ray_crystal_structure_of_(C5H4SiMe_3)2Zr(PPh2)2 [accessed Nov 26, 2015].We thank D. de Montauzon for pertinent discus­\ud sions and the Action Integree France-Espagne (Grant No. 106-1989) for generous support to J.C.F. and\ud A.M.L. and CICYT for financial support to Dept. Q.\ud Inorganica (Project PB 89/0208)