Hydride complexes clusters

One of the limitations of both 4 and 7 in catalysis is their ready decomposition to inactive cluster hydride complexes in the absence of substrate. If the substrate is a weak ligand (e.g., Me2C=CMe2), this decomposition can be competitive with cluster formation. A high concentration of substrate favors catalysis... 

Neutron Diffraction Studies of Tetrahedral Cluster Transition Metal Hydride Complexes HFeCo3(CO)9-(P(OCH3)3)3 and H3Ni4(C5H5)4... 

In the report that described the synthesis of 108 (777), Whitmire also observed that the reaction between NaBi03 and methanolic [Fe(CO)s] in the presence of hydroxide afforded the trianionic species [Bi Fe(CO)4 4]3, 110, which was subsequently characterized by X-ray crystallography (775). Cluster 110 contains a central bismuth atom tetrahedrally coordinated by four Fe(CO)4 fragments and is isoelectronic with the anionic tetracobalt-indium complex, 27, and the neutral tetracobalt-germanium, - tin, and -lead complexes, 68, 71, and 72. Oxidation of 110 affords 108 (777), while acidification (772) yields the hydride-containing cluster [BiFe3(CO)9(/i-H)3], 111, which also contains a tetrahedral BiFe3 core. Johnson and Lewis (114) have... 

Other noteworthy trinuclear hydride complexes include HMn3(CO)10(BH3)2 121>, a rare cluster containing both M-H-M and M-H-B bridges (Fig. 25), and the com-... 

Reaction of the rhenium hydride complex ReH7(PR3)2 (where R = Ph or p-tol) with Au(PPh3)N03 has yielded the heteronuclear cluster compounds [Au5Re(H)4(PR3)2(PPh3)5](PF6)2 (148) in which the metal cores are based on edge-shared bitetrahedra with the rhenium atom at one of the two most-connected vertices. This is illustrated in Fig. 24. A... 

Apart from hydridoruthenium carbonyl cluster compounds (see Sections 45.10.3.3 and 45.10.4) the only Ru° hydride complexes are the deep brown [RuH(NO)(PR3)3] (R3 = Ph3, Ph2Me, Ph2Pr , Ph2Cy) w hich are fully discussed in Section 45.5.1.2. 

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