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Transition metal complexes with sulfur ligands. XXXI. Six and seven coordinate CO, NO, PMe3 and phosphineiminato molybdenum complexes with [Mo{S4}] frameworks ({S4}=2, 3; 8, 9-dibenzo-1,4, 7,10-tetrathiadecane( 2 -))

1988; Elsevier BV; Volume: 141; Issue: 2 Linguagem: Inglês

10.1016/s0020-1693(00)83916-x

1873-3255

Dieter Sellman, J. Keller, Matthias Moll, Charles F. Campana, Martin Haase,

Metal-Organic Frameworks: Synthesis and Applications

In order to explain the high reactivity of [Mo- (NO)2(dttd)] towards phosphines the structures of [Mo(CO)2(PMe3)(dttd)] and [Mo(NO)(NPMePh2)- (dttd)] have been determined by X-ray structure analysis and compared with the structures of other [M(dttd)] complexes (dttd2-=2,3;8,9-dibenzo- 1,4,7,10-tetrathiadecane(2-)). In [Mo(CO)2(PMe3)- (dttd)] the seven coordinate Mo center is ligated by one P, two C and four sulfur atoms. [Mo(NO)(NP- MePh2)(dttd)] contains a six coordinate molybenum atom pseudooctahedrally surrounded by two N and four S atoms and possesses a bent [MNP] entity with an exceedingly small angle of 129.7(4)°; the pseudooctahedral [MS4] core in [M(dttd)] fragments is flexible enough to accommodate the coordination of two as well as three further coligands. The reaction between [Mo(NO)2(dttd)] and phosphines PR3 yielding the phosphineiminato complexes [Mo(NO)- (NPR3)(dttd)] is dominated by the nucleophilicity of PR3 as is shown by the fast reactions with PMe3 and PCy3 and the slow reactions with arylphosphines. [MNP] angles and νas(MNP) frequencies in [M- (phosphineiminato)] complexes correlate: small angles compare with low frequencies. 13C, 95Mo and 14N NMR data of the complexes are discussed and indicate the oxidation of Mo and the reduction of the nitrogen of one NO ligand, when [Mo(NO)2- (dttd)] is converted into [Mo(NO)(NPR3)(dttd)]; NPR3 ligands act as strong 4e- donors.