Transition metal complexes bridging ligands

Electron-beam heating, in metal vapor synthesis, 1, 232 Electron-beam vaporization, in metal vapor synthesis, 1, 224 Electron correlation, and computational chemistry, 1, 642 Electron counting, in transition metal complexes bridging ligands, 1, 14 examples, 1, 9 ligand electrons, 1, 5/... 

Transition metal complexes with bridging hydride ligands. L. M. Venazi, Coord. Chem. Rev., 1982, 43, 251-274 (40). 

The finding of preparatively available iminoboranes RB = NR some years ago opened exciting new possibilities not only in B—N chemistry, but also in coordination chemistry. The first examples of iminoborane-transition-metal complexes have now been published. The structurally completely characterized t-BuB = NBu-t adds, like its alkyne analog, to the 03(00)5 fragment as a bridging ligand. When Co2(CO)g and t-BuB = NBu-t are dissolved in pentane at 0°C, warming to RT and evaporation of unreacted iminoborane yields (t-BuBNBu-t)Co2(CO)5 (86%) as a black solid, which can be recrystallized from ether-nitromethane (1 3) ... 

A chiral diphosphine ligand was bound to silica via carbamate links and was used for enantioselective hydrogenation.178 The activity of the neutral catalyst decreased when the loading was increased. It clearly indicates the formation of catalytically inactive chlorine-bridged dimers. At the same time, the cationic diphosphine-Rh catalysts had no tendency to interact with each other (site isolation).179 New cross-linked chiral transition-metal-complexing polymers were used for the chemo- and enantioselective epoxidation of olefins.180... 

As yet, with regard to both ligands C(NHC)2 and C[C(NMe2)2 2. each is only represented by one transition metal complex. The two complexes are confirmed by X-ray analyses. The carbodicarbene C(NHC)2 was allowed to react with [Rh(p-Cl) (CO)2l2 to afford complex 70 in benzene solution. The carbon is able to split the chlorine bridge in the starting Rh complex and the vacant coordination site is occupied by the ligand, a very common synthetic route [10, 11]. 

Bridging ligands, 32 56 Fe—S clusters, 38 172 Bridging oligopyridines, 30 72-73 Bridging tetrazadiene, in transition metal complexes, 30 43, 48, 49... 

The best enantioselectivity (35% ee) was observed in the reaction of l-(l-naphthyl)-2-propyn-l-ol with acetone in the presence of a complex bearing a 1-naphthylethylthio-lato moiety as a chiral ligand. Although the enantioselectivity is not yet satisfactory, this was the first example of an enantioselective propargylic substitution reaction catalyzed by transition metal complexes [27]. It is noteworthy that the chiral thiolate-bridged ligands work to control the chiral environment around the diruthenium site. 

Multiple metal-metal bonds have since been found in Re and many other transition metal complexes [41]. The structure of the unsupported Re2 unit (2) is shown in Chart 1. Bonds to the ligands in the equator around each metal may be staggered or eclipsed depending on electronic structure, and solvent or unidentate ligands may bind weakly at the axial positions. In some cases, polydentate ligands may bridge the metal-metal-bonded unit (3). 

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