COORDINATION PROPERTIES OF SILVER DIPHOSPHINE COMPLEXES - CRYSTAL-STRUCTURES AND MOLECULAR-STRUCTURES OF AG(2)X(2)(M-PP)(2) (X=I, CL, NO3 M-PP=1,3-BIS[(DIPHENYLPHOSPHINO)METHYL]BENZENE) AND AG(2)X(2)(O-PP)(2) (X=I CL O-PP=1,2-BIS[(DIPHENYLPHOSPHINO)METHYL]BENZENE) - SYNTHESIS AND H-1-NMR AND P-31-NMR SPECTROSCOPY OF SILVER DIPHOSPHINE COMPLEXES

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.