Phosphane ligand

The versatility of tertiary phosphane ligands in coordination and organometallic chemistry. R. Mason and D. W. Meek, Angew. Chem., Int. Ed. Engl., 1978,17,183-194 (138). 

Many chiral phosphorus ligands have shown excellent reactivities and enantio-selectivities in the Rh-catalyzed hydrogenation of itaconic acids or esters. Some successful (>95% ee) hydrogenations of itaconic acid or its dimethyl ester with different chiral phosphorus ligands are listed in Table 26.7. High reactivity is observed with electron-rich phosphane ligands such as BICHEP [7c[. 

Phosphite ligands (Fig. 9) are known to be better 7r-acceptors than phos-phane ligands. The stronger electron-withdrawing ligand increases the reaction rate because CO from the metal center is dissociated faster than with phosphane ligands. For different mono-phosphites, the selectivity to the... 

The presence of the P4 molecule was indicated by osmometric molecular weight determinations, mass spectrometry, and by the easy displacement, even at -78°C, of the intact P4 unit by carbon monoxide or phosphane ligands. The infra-red and Raman spectra showed bands attributable to a bound P4 molecule under 3 or Cg... 

Scheme 1 Carbo-vasnc versions of carbonyl and phosphane ligands...

Carbodiphosphoranes C(PR3)2 and related ligands CL2 which are also termed double ylides differ from the other carbon ligands which are discussed in this volume in the number of lone electron pairs at the carbon donor atom. Ylides, carbenes, allenylidenes, and cumulenylidenes have one lone electron pair but carbodiphosphoranes have two lone electron pairs with a and n symmetry. The bonding situation in a carbodiphosphorane (a special class of CL2 compounds, abbreviated as CDP) is best described in terms of donor-acceptor bonding between the phosphane ligands which serve as a donor and a naked carbon atom in an... 

Catalytic enantioselective synthesis of 4,4-dimethyl-l-phenyl-l,2-pentadiene from 4,4-dimethyl-1,2-pentadiene and iodobenzene using 0.4 to 1 mol % of palladium complexes containing chiral phosphane ligands as the catalyst for the enantioselective cross coupling134 is the only example of substoichiometric transition metal catalyzed enantioselective allene synthesis. 

The range of carbon nucleophiles that have been successfully employed for 1,4-addition to -a,/i-unsaturated iron-acyl complexes is limited to simple alkyl- and aryllithium species. Grignard reagents and the 1,3-propanedioate anion are reported to fail to react with. E-complexes36. The effect of varying the phosphane ligand has been examined little effect upon... 

---