作者:Joel T. Mague、Zhaiwei Lin
DOI:10.1021/om00060a034
日期:1992.12
The use of cpFeCl(PNP)2 and Mo(CO)3(PNP)2 (CP = cyclopentadienyl; PNP = MeN(PF2)2) as precursors to heterobimetallic complexes is reported. The former generally reacts via chloride transfer to low-valent metal complexes while the latter either gives heterobimetallic complexes bridged by two PNP ligands or acts as a source of PNP ligands. cpFeCl(PNP)2 With CO2(CO)8 gives CoCl2 and cpFe(mu-PNP)2Co(CO)2 (1) and with Pt(C2Ph2)(PPh3)2 forms PtCl(PPh3)(mu-PF2)(mu-PF2NMe)Fe(PF2NHMe)cp (2) and PtCl(P-(O)F2)(PPh3)2 (7). The last is also formed from PNP and PtCl2(PPh3)2. MO(CO)3(PNP)2 with Ni-(CO)2(PPh3)2 or Pt(C2H4)(PPh3)2 gives MO(CO)3(mu-PNP)2M(PPh3) (M = Ni (3), Pt (4)) while with MCl(CO)(PPh3)2 the products are MO(CO)3(mu-PNP)2IrCl(CO)(PPh3) (M = Ir, 5) and MO(CO)3(mu-PNP)2RhCl(PPh3) (M = Rh, 6). Direct reaction of PNP with Pt(C2H4)(PPh3)2 and CP2Mo2(CO)4 yields Pt2(mu-PNP)3(PPh3) (8) and cp2Mo2(CO)4(mu-PNP) (9), respectively. The P-31 NMR spectra of the complexes and related chemistry are discussed. The crystal structures of 1, 2, 4, 7, and 8 have been determined by X-ray crystallography. 1: monoclinic; P2(1)/n; a = 8.750 (1), b = 19.908 (2), c = 10.719 (2) angstrom; beta = 95.97 (1)-degrees-; Z = 4. 2: monoclinic; P2,/c; a = 12.696 (2), b = 13.479(2), c = 21.031 (1) angstrom; beta = 92.620 (7)-degrees; Z = 4. 4: orthorhombic; Pbca; a = 14.544 (1), b = 23.023 (1), c = 19.453 (2) angstrom; Z = 8. 7: monoclinic; P2(1)/c; a = 11.828 (2), b = 20.678 (4), c = 8.317 (1) angstrom; bet = 95.04 (1)-degrees; Z = 2. 8: monoclinic; P2(1)/c; a = 11.696 (2), b = 16.492 (2), c = 17.809 (2) angstrom; beta = 103.465 (2)-degrees; Z = 4.