Hydrido complexes, octahedral

Another synthetic approach to the octahedral complexes of type (252) is provided by the thermal decomposition of the hydrido complex [ReH7(PPh3)2] in the presence of 2-mercapto-quinoline or 2-hydroxyquinoline in 1,2-dichloroethane solutions. The solvent is source of the chloro ligands and, thus, essential for the formation of the rhenium(III) products. Comparable reactions in THF afford hydridorhenium(V) complexes (see Section 5.3.2.11). 

In both compounds the iron atom geometries can be described as intermediate between octahedral and bicapped tetrahedral, but in the hydrido complex the H-Fe-H bond angle is 100°, whereas the Au-Fe-Au bond angle is only 73°. This smaller angle leads to an Au-Au distance of3.028(1) A, which is indicative of a weak interaction between the gold atoms. 

With NH3 or amines, quite stable octahedral hydrido complexes can be obtained for rhodium. Thus the reduction of RhCl3-3H20 in NH4OH by Zn in the presence of S04 leads to the white, air-stable, crystalline salt [RhH am5]S04. In aqueous solution the ion hydrolyzes ... 

The trinuclear zirconocene-aluminum heterometallic hydrido complex [Cp2ZrH(//-H)2]3Al 652 was isolated in low yield from the reaction of Cp2ZrCl2 with LiBH4, LiAlH4, and a catalytic amount of Cp2TiCl2 (Equation (40)). The molecular structure of this complex has been determined by X-ray diffraction analysis, featuring the distorted octahedral Al geometry.474... 

Complexes with other Carbon-donor Ligands. The naphthyl hydrido Complexes of the type [MH(CioH,)(MejP CHg CHa-PMe2)2] (46), where M = Ru or Os , are isomorphous and isostructural. They are octahedral and contain a naphthyl ligand o-bonded to the metal atom and in a position cis to the hydrido hydrogen. The respective Ru-C, Os-C, and Ru-H distances are 2.16(1), 2.13(2), and 1.7 A in the osmium compound the hydrido hydrogen atom has not been located. The M-P distances range... 

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