FULVALENE TITANIUM AND ZIRCONIUM COMPLEXES - SYNTHESIS AND NMR-STUDY OF PHOSPHANIDO-DERIVATIVES, ALKYL-DERIVATIVES, AND ALKYNYL-DERIVATIVES - X-RAY CRYSTAL-STRUCTURES OF [(TI(ETA(5)-C5H5)(MU-PPH(2)))(2)(MU-(ETA(5)-C5H4-ETA(5)-C5H4))] AND [(ZR(ETA(5)-C5H5)(MU-C-CSUME(3)))(2)(MU-(ETA(5)-C5H4-ETA(5)-C5H4))]

Reaction of [{M(eta(5)-C5H5)(mu-Cl)}(2){mu-{eta(5)-C5H4-eta(5)-C5H4)}] (M = Ti, 1; Zr, 2) or [{M(eta(5)-C5H5)Cl-2}(2){mu-{eta(5)-C5H4-eta(5)-C5H4)}], (M = Ti, 5; Zr, 6) with one or two equivalents of LiPPh(2) afforded the new phosphanidometal(III) complexes [{(M(C5H5)(mu-PPh(2))}(2){mu-(eta(5)-C5H4)}], 5-C,H,))1, (M = Ti, 3; Zr, 4). Reaction of 2 with LiC drop CSiMe(3) led to the diamagnetic zirconium(III) alkynyl derivative [{Zr(C5H5)(mu-C drop CSiMe(3))}(2)(mu-eta(5)-C(5)H4-eta(5)-C5H4], 7. Alkylation of 6 with LiCH(2)CMe(2)Ph gave [{Zr(eta(5)-C5H5)(CH(2)CMe(2)Ph)(2)}(2){mu-(eta(5)-C5H4-eta 5-C5H4)}], 8. A detailed NMR study of complexes 3 and 4 allowed the observation of the spectral behaviour of the eight different fulvalene protons through their coupling to the P-31 nucleus. The fluxional behaviour of complex 7 was studied by dynamic DNMR, and kinetic parameters for the sigma-pi-conversion of the alkynyl ligand were determined. The molecular structures of complexes 3 and 7 were determined by X-ray diffraction methods.