Isocyanide ligands hydrides

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. 

These kinds of studies have been restricted to carbon monoxide ligands, hydride ligands and some organic ligands as isocyanides. With carbon monoxide the ligand migration may occur between ... 

Complexes Containing Hydride, Carbonyl, and Isocyanide Ligands... 

Interestingly, co-ordination of isocyanide ligand to the endo-hydride olefin tantalum complexes gives adducts containing organic groups [equation (6)]. ... 

The chromium(II) hydride [CrH2 P(OMe)3 s] is fluxional and the seven-coordinate structure (20) is likely from an analysis of the 31P and XH NMR spectra (Table 21).125 Some mixed ligand complexes with organic isocyanides are given in Table 3. 

Os3H2(CO)10(PPh3) (64, L = PPh3) (553), and Os3H2(CO)10 ( BuNC) (65, R = Bu) (354) in the crystal have been determined. The structures relate closely to that of Os3(CO)12 with an axial terminal hydride replacing one CO ligand. As with substitution derivatives of Os3(CO)12, bulky ligands like tertiary phosphines are equatorial while hydride and isocyanides are axial. Two axial isomers are possible, 65 and 66. Both are present in solution but the trans isomer (65) is crystallized. 

Another class of heteroleptic alkyl complexes contains 7t-donating ancillary ligands such as RU[N(Si(CH3)3)2]3 (R = CH3, H, BH ). The hydride species can be converted into the methyl species via reaction with BuLi and CH3Br. The methyl compound has exhibited insertion chemistry with small molecules including aldehydes, ketones, nitriles, and isocyanides (206). Stable metallacyde compounds are also known, ie,... 

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