Tertiary Phosphines and Related Ligands

Reaction of lMn(R)(CO)J with Tertiary Phosphines and Related Ligands... 

Complex hydrides with tertiary phosphines and related ligands... 

Functionalized Tertiary Phosphines and Related Ligands in Organometallic Coordination Chemistry and Catalysis... 

A linear correlation is reported between 8p(phosphine) and the change in chemical shift that occurs upon co-ordination of tertiary phosphines with a number of transition metals. The half-neutralization potential, the Taft a, and Sp of the complexes of tertiary phosphines and titanium tetrachloride have been found to be related. The equilibria involving the co-ordination of phosphoryl compounds and water with metal ions such as Al + are sufficiently slow to be studied by n.m.r. and P n.m.r. spectroscopy. Discrete signals from co-ordinated and unco-ordinated ligands are observed. Where this does not occur the equilibrium constant can be estimated from a plot involving chemical shift and concentration of reactant. ... 

The coordination chemistry of tertiary phosphine-functionalized calix[4]arenes have been described.279 Treatment of a bis(diphenylphosphino) or bis(dimethylphosphino) derivative of calix[4]arene with [PtCl2(COD)] leads to the formation of the corresponding dichloroplatinum(II) complex. The related diplatinum(II) species has also been reported with the tetrafunctionalized calix[4]arene.280 The mononuclear derivative is susceptible to oligomerization if the two free phosphine ligands are not oxidized or complexed to another metal center such as gold(I).279 The platinum(II) coordination chemistry of a mono-281 and diphosphite282 derived calix[ ]arene (n = 4 and 6, respectively) has also been described. 

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. 

---