Synthesis and coordination chemistry (with platinum(II) and molybdenum(0)) of new bis(bis(trifluoromethyl)phosphano)alkanes. Structure of a new bis(phosphano)methanide complex

Two known and four new bis(phosphano)alkanes (CF3)2P(CH2)/sub n/P(CF3)2, n = 1-3; [(CF3)2PCR(CH3)P(CF3)2, R = H, CH3; (CF3)2P(CF2)2P(CF3)2] have been prepared in good yield by an improved procedure. PtCl2 and Mo(CO)4 complexes of these highly π-acidic ligands have been prepared by standard routes. Thus, displacement of benzonitrile from [PtCl2(PhCN)2] affords [PtCl2LL][LL = (CF3)2P(CH2)/sub n/P(CF3)2, n = 2,3; LL = (CF3)PCR(CH3)P(CF3)2, R = H, CH3; LL = (CF3)2P(CF2)2P(P)(CF3)2]. Similarly, piperidine is displaced from cis-[Mo(CO)4(piperidine)2] to give [Mo(CO)4(LL)], (LL = (CF3)2P(CH2)/sub n/P(CF3)2, n = 2,3; LL = (CF3)2P(CF2)2P(CF3)2). Self-dehydrochlorination of [PtCl2[(CF3)2PCH(CH3)P(CF3)2]] in the solid state at 150/degrees/C gives the complex [Pt2(μ-Cl)2[(CF3)2PC(CH3)P(CF3)2]2] (34), shown by single-crystal X-ray crystallography to contain two chelating bis(phosphano)methanide ligands. The crystal parameters of 84 are reported. 47 references, 4 figures, 8 tables