Publication Details (including relevant citation information):
Todd W. Graham, Angela Llamazares, Robert McDonald,† and Martin Cowie
Organometallics, 1999, 18 (17), 3490
The syntheses of a series of bifunctional ligands, in which a cyclopentadienyl and a phosphine group are linked by either a CH2 or a C2H4 fragment (-C5H4(CH2)nPR2; n = 1, 2; R = Me, Ph), are reported, as is that of the related ligand, Li2[Me2C(C5H3CMe2PPh2)2], in which both substituted cyclopentadienyl rings are linked by the CMe2 group. The metallocene dichloride complexes Cp‘2MCl2 (M = Ti, Zr; Cp‘2 = 2C5H4(CH2)nPPh2 (n = 1, 2), Me2C((C5H3)C(Me)2PPh2)2) have also been prepared, and the X-ray structure of (η5-C5H4(CH2)2PPh2)2ZrCl2 (7) has been determined. This complex has the pendent phosphinoalkyl arms close to eclipsed on the two C5H4 groups and bisecting the ZrCl2 angle, but bent in opposite directions away from the ZrCl2 plane. Reaction of 7 and its Ti analogue with (COD)Mo(CO)4 yields the heterobinuclear complexes [(μ-η5:η1-C5H4(CH2)2PPh2)2MCl2Mo(CO)4] (M = Ti, Zr). Structure determinations of these bimetallic complexes show the expected cis arrangement of phosphine moieties at Mo, M−Mo separations of 6.895 Å (M = Ti) and 6.945 Å (M = Zr), and MCl2 moieties aimed at right angles to the M−Mo vectors.
Address (URL): http://pubs.acs.org/doi/abs/10.1021/om990279w