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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)

✍ Scribed by D. K. Johnson; P. S. Pregosin; L. M. Venanzi

Publisher: John Wiley and Sons
Year: 1976
Tongue: German
Weight: 729 KB
Volume: 59
Category: Article
ISSN: 0018-019X
DOI: 10.1002/hlca.19760590808

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✦ Synopsis

Sunznzary. The preparation of monomcric complexes [MX(l)] is reported where 1LI. = Cu, Ag, Au; X = I, C1, 7 3 0 3 , BF4 and 1 = 2,ll-bis(diphenylphosphinomethyl)benzo[c]phenanthrene.

The solution structure of the complexes is discussed on the basis of molecular weight, conductivity and NMR. measurements. I n acetonitrile and nitromethane, thc nitrate and fluoroborate complexes exist as ionic species [M(l)] fXwhereas the halo-complexes are present as equilibrium mixtures of 'covalent' and 'ionic' forms. All the complexes are associated in CHzClz-solutions.

The values of 1J107Ag-31p show that this association in [Ag(N03) (l)] and [Ag(BF4) (l)] is best described in terms of ion-pairing while that for species [AgX(l)] (X = C1, Br and I) is mainly 'covalent' in nature. Evidence is presented for the formation of the complex ion [Ag(CH&N),(l)]+ in acetonitrile solution.

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