Heterobimetallic complexes of rhenium and ruthenium containing methylaminobis(difluorophosphine)

Article abstract of DOI:10.1021/om00020a019

The syntheses of cpRuCl(η¹-MeN(PF₂)₂)₂ (1) and fac-ReBr(CO)₃(η¹-MeN(PF₂)₂) ₂ (3) are described together with their use in the directed synthesis of heterobimetallic complexes. The monodentate MeN(PF₂)₂ ligands in 1 are cleaved on exposure to moisture or on chromatography on Florisil to give cpRu(P(O)F₂)(PF₂NHMe)₂ (2). With Co₂(CO)₈ 1 and 3 respectively yield cpRu(μ-MeN(PF₂)₂)₂Co(CO)₂ (4) and fac-Re(CO)₃(μ-MeN(PF₂)₂) ₂Co(CO)₂ (5), while with IrCl(CO)(PPh₃)₂, cpRu(μ-MeN(PF₂)₂)₂IrCl₂(PPh ₃) (6) and fac-Re(CO)₃(μ-MeN-(PF₂)₂) ₂IrClBr(PPh₃) (7) are obtained. Complex 1 and [RhCl(CO)₂]₂ yield cpRu(μ-MeN(PF₂)₂)₂-RhCl₂ (8) which adds dimethylphenylphosphine to give cpRu(μ-MeN(PF₂)₂)₂RhCl₂(PMe ₂Ph) (9) while with 3 the product is fac-Re(CO)₃(μ-MeN(PF₂)₂)₂RhClBr (10). A complex mixture of products is formed from 1 and Pt(L)(PPh₃)₂ (L = C₂H₄, C₂Ph₂) which has not been completely characterized, but fac-Re(CO)₃(μ-MeN(PF₂)₂) ₂PtBr(PPh₃) (11), in which the platinum adopts a distorted square pyramidal coordination with a very long apical Pt-Br bond, is obtained from 3 and Pt(C₂Ph₂)(PPh₃)₂. The structures of 2, 5, 9, and 11 have been determined by X-ray crystallography. 2: monoclinic; P2₁/n; a = 10.487(2), b = 11.832(2), c = 11.910(2) A?; β = 90.50(1)°; Z = 4. 5: triclinic; P1; a = 9.794(1), b = 10.563(1), c = 9.624-(2) A?; α = 98.06(1), β = 101.29(1), γ = 81.796(9)°; Z = 2. 9: monoclinic; P2₁/c; a = 18.239-(3), b = 8.195(2), c = 18.078(2) A?, β = 102.36(1)°; Z = 4. 11: monoclinic; C2/m; a = 12.649(2), b = 14.908(1), c = 19.798(2) A?; β = 96.600(9)°; Z = 4.