Heterobimetallic complexes containing methylaminobis(difluorophosphine)

Article abstract of DOI:10.1021/om00060a034

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(μ-PNP)₂Co(CO)₂ (1) and with Pt(C₂Ph₂)(PPh₃)₂ forms PtCl(PPh₃)(μ-PF₂)(μ-PF₂NMe)Fe(PF ₂NHMe)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 Pt(C₂H₄)(PPH₃)₂ gives Mo(CO)₃(μ-PNP)₂M(PPH₃) (M = Ni (3), Pt (4)) while with MCl(CO)(PPH₃)₂ the products are Mo(CO)₃(μ-PNP)₂IrCl(CO)(PPh₃) (M = Ir, 5) and Mo(CO)₃(μ-PNP)₂RhCl(PPh₃) (M = Rh, 6). Direct reaction of PNP with Pt(C₂H₄)(PPh₃)₂ and cp₂Mo₂(CO)₄ yields Pt₂(μ-PNP)₃(PPh₃) (8) and cp₂Mo₂(CO)₄(μ-PNP) (9), respectively. The ³¹P 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; P2₁/n; a = 8.750 (1), b = 19.908 (2), c = 10.719 (2) A?; β = 95.97 (1)°; Z = 4. 2: monoclinic; P2₁/c; a = 12.696 (2), b = 13.479 (2), c = 21.031 (1) A?; β = 92.620 (7)°; Z = 4. 4: orthorhombic; Pbca; a = 14.544 (1), b = 23.023 (1), c = 19.453 (2) A?; Z = 8. 7: monoclinic; P2₁/c; a = 11.828 (2), b = 20.678 (4), c = 8.317 (1) A?; β = 95.04 (1)°; Z = 2. 8: monoclinic; P2₁/c; a = 11.696 (2), b = 16.492 (2), c = 17.809 (2) A?; β = 103.465 (2)°; Z = 4.