Transition‐Metal Complexes with Bidentate Ligands Spanning trans‐Positions. III. Preparation and solution studies of complexes [MX(1)] (M = Cu, Ag and Au; X = anionic ligand; 1 = 2, 11‐bis(diphenylphosphinomethyl)benzo[c]phenanthrene)

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Abstract
The preparation of monomeric complexes [MX(1)] is reported where M = Cu, Ag, Au; X = I, Cl, NO3, BF4 and 1 = 2,11‐bis(diphenylphosphinomethyl)benzo[c]phenanthrene. The solution structure of the complexes is discussed on the basis of molecular weight, conductivity and NMR. measurements. In acetonitrile and nitromethane, the nitrate and fluoroborate complexes exist as ionic species [M(1)]+X− whereas the halo‐complexes are present as equilibrium mixtures of ‘covalent’ and ‘ionic’ forms. All the complexes are associated in CH2Cl2‐solutions. The values of 1J show that this association in [Ag(NO3) (1)] and [Ag(BF4) (1)] is best described in terms of ion‐pairing while that for species [AgX(1)] (X = Cl, Br and I) is mainly ‘covalent’ in nature. Evidence is presented for the formation of the complex ion [Ag(CH3CN)n(1)]+ in acetonitrile solution.

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