Binuclear groups

The path followed by the hydrogenation reactions catalyzed by the mono-/A-hydrides (2a and 2b) is not so clear, but the kinetic data strongly suggest that the binuclear grouping is retained, at least during the early stages of reaction. A possible first step is the formation of a rearranged complex, such as (A), proposed for the stoichiometric reaction with dienes. 

Scheme 83. Binuclear Group 6 chalcoacyl complexes (L = / -7,8-C2B9Hii R = C6H4Me-4 M = Mo, W ...

Other common species with this mode of coordination are the binuclear group 9 (VIII) complexes [M2(S2CNR2)5]" ", formed upon oxidation of tris(-dithiocarbamate) complexes, [M(S2CNR2)3] (M = Co, Rh) (Eq. 45) (302-311). 

In nickel and palladium dithiobenzoato complexes, four-membered chelate rings are formed (366), whereas, in the corresponding phenyl-dithio acetates [M2(S2CCH2Ph)4], the dithio ligands act as bridging groups between the two metal atoms, with the formation of binuclear units (367). The molecular structure of the latter compounds shows that each metal atom is coordinated to four sulfur atoms and to the other metal atoms in a square-pyramidal geometry. Other evidence for... 

Ethers in which at least one group is primary alkyl can be oxidized to the corresponding carboxylic esters in high yields with ruthenium tetroxide. Molecular oxygen with a binuclear copper (II) complex " or PdCVCuCVCO " also converts ethers to esters. Cyclic ethers give lactones. " The reaction, a special case of 19-14,... 

The first complexes of a-keto ylides and group 5 early transition metals have only recently been obtained by reaction of Nb(III) derivatives [[NbCl3(dme) (R C=CR")] with 25 (R = thiazolyl) (Scheme 16). The chelation of the ylide occurs through an N,0-coordination to the metal center and in presence of MeLi a deprotonation of a phenyl ring takes place with the loss of alkyne, leading to the formation of a new orfho-metallated binuclear compound 32. The two ylides involved in the complexation behave as tridentate anionic ligands and are mutually in a trans disposition in order to minimize the steric hindrance [71,72]. Another binuclear niobium complex 33 has been obtained from 25 (R = Me, Ph) with this time an 0-coordinated a-keto ylide [68]. 

The great majority of platinum(I) complexes are binuclear with monofunctional or bifunctional bridging groups. However, there is also a series of unsupported dimers with the general structure shown in (12). These are generally stabilized by phosphine, carbonyl, and isocyanide ligands.17 Dimeric hydride complexes can have terminal or bridging hydrides and these are discussed above in Section 6.5.2.1.4. 

Compounds 4-7 (Table 1) belong to this group. The physicochemical properties of the given binuclear clusters are close to those of the analogous rhenium and molybdenum compounds with the quadruple M-M bonds and are as a rule isostructural with them [1,89,90]. 

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