The synthesis and H-1- and P-31-NMR spectra of silver halides and silver nitrate complexes of the ligands 1,3-bis[(diphenylphosphino)methyl]benzene (m-PP) and 1,2-bis[(diphenylphosphino)methyl]benzene (o-PP) are reported. The crystal and molecular structures of Ag(2)X(2)(m-PP)(2)(X = I, Cl, NO3) and Ag(2)X(2)(o-PP)(2)(X = I, Cl) show that these complexes are binuclear with a rhomboid core consisting of two metals and two anionic ligands. The metal is tetrahedrally surrounded by the two bridging anions and two P atoms. For m-PP complexes, each Ag atom is bound to P atoms of different phosphines which also act as bridging ligands. On the other hand, the o-PP ligand coordinates in a chelate fashion. This difference in behavior is related to the length of the chain between the phosphine donors, wh;ich determines whether chelation can occur in complexes of composition AgX-(o-PP). The bond angle P-Ag-P, ranging from 110 to 138 degrees, is related to the nucleophilicity of the anions. In the m-PP complexes, the shape of the rhomboid core is strongly influenced by the van der Waals interactions of the core atoms. Crystal data are as follows: Ag2I2(m-PP)(2), monoclinic, P2(1)/c, Z = 4, a = 12.082(4)Angstrom b = 22.536 (9) Angstrom, c = 22.438(5) Angstrom, beta = 104.22(2)degrees, Ag2Cl2(m-PP)(2), triclinic, P (1) over bar,Z = 2, a = 12.307(3) Angstrom, b = 12.704(3) Angstrom, c = 19.673(5) Angstrom, alpha = 90.02(2)degrees, beta = 104.55(2)degrees, gamma = 96.97(2)degrees; Ag-2(NO3)(2)(m-PP)(2), triclinic, P (1) over bar, Z = 2, a = 12.303(6) Angstrom; b = 12.953(9) Angstrom, c = 19.572(8) Angstrom, alpha = 88.89(5)degrees, beta = 74;13(3)degrees, gamma = 80.95(5)degrees; Ag2I2(o-PP)(2), monoclinic, P2(1)/a, Z = 2, a = 14.542(2) Angstrom, b = 16.828(3) Angstrom, c = 12.857(2) Angstrom, beta = 70.71(1)degrees; Ag2Cl2(o-PP)(2), monoclinic, P2(1)/a, Z = 2, a = 14.046(4) Angstrom, b = 16.882(3) Angstrom, c = 12.845(5) Angstrom, beta = 68.63(3)degrees.

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AbstractThe preparation of complexes [MX2(1)] (M = Ni, Pd, and Pi; X ‐ Cl, Br, and I; 1 = 1,2‐bis[(diphenylphosphino)methyl]benzene). [Pt(OSO2CH3)Et(1)], [Pt(alkene)(1)] (alkene ‐ C2H2, and CH2 = CHCN), and [(1)Pt‐(μ‐H)2PtH(1)][BPh4] is reported. Their 1H‐ and 31P‐NMR spectra were recorded and used lor structural assignments. The X‐ray crystal structure of [Pt(C2H4)(1)] was determined. It is shown that the PPtP bond angle in this complex differs significantly from those found in related compounds with monodentate phosphines, and that this difference is likely to be due to intramolecular contacts.

The coordination chemistry of the ligands 1,2-and 1,3-(Ph2CH2)2C6H3, 1 and 2, with Ni(II), Pd(II), Pt(II), Rh(I), Cu(I) and Ag(I) is described.

The preparations of the binuclear hydrido-bridged cations [(terdentate ligand)Pd(μ-H)Pd(terdentate ligand)]+ from [(terdentate ligand)Pd(acetone)]+ and NaO2CH and [(terdentate ligand)Pd(μ-H)Pt(terdentate ligand)]+ from [(terdentate ligand)Pd(acetone)]+ and [(terdentate ligand)PtH] (terdentate ligand = 2,6-(Ph2PCH2)2C6H3) are reported. The preparation of the cation [(terdentate ligand)Pt(μ-H)Pt(terdentate ligand)]+ is also reported.

It is shown that 1,3-bis(diphenylphosphinomethyl)benzene (PCHP) readily undergoes a cyclometallation reaction with nickel(II), palladium(II), and platinum(II) species giving products of the type [MX(PCP)] [M  Ni, Pd, and Pt; X  halide and PCP  2,6-bis(diphenylphosphinomethyl)phenyl]. Cyclometallation requires the formation of intermediates trans-[MX2(PCHP)].