Phosphine Chalcogenides as Ligands

4 Phosphine Chalcogenides as Ligands. - The complexation of lanthanide and actinide ions by phosphine oxide ligands remains an active area, and a theoretical assessment of the coordination of phosphine oxides (and phosphate esters) by trivalent lanthanide ions has appeared. Trivalent lanthanide complexes of the functionalised enol phosphine oxide (265), (and a related phosphonate), have been describedComplexes of thorium(iv) with bis(di-phenylphosphino) ethane dioxide and bis(diphenylphosphinoyl)amide have also been characterised. Calixarene systems which bear phosphine oxide 

Tributylphosphine sulfide has been used as a co-catalyst with dicobalt octacarbonyl for the Pawson-Khand reaction. Thermolysis of a mixture of cadmium chloride and trioctylphosphine sulfide at 250 °C has been used as a route to the formation of nanocrystalline cadmium sulfide. A complex of triphenylphosphine sulfide with a silver-tungsten-iodine acceptor has been characterised by X-ray studies. Ferrocenylphosphine chalcogenides have attracted considerable interest as ligands. Complexes of the monophosphino-phosphine sulfide (269) with rhodium have been characterised. The disulfide (270) forms complexes with both gold(i) and gold(iii) acceptors, and a silver(i) complex of the diselenide (271) has been prepared.  

2 Reactions. - The phosphonium salts (287) have been shown to undergo facile nucleophilic displacement of triphenylphosphine on treatment with a range of C, N and S-nucleophiles, giving a range of functional P-substituted silyl enol ethers. The 4-phosphonio-oxazolones (288) undergo dephospho- 

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Phosphine Chalcogenides as Ligands. - The enhanced stability provided by two triphenylphosphine oxide ligands has enabled the first crystal structure analysis of a non-haem-di-iron-dioxygen adduct. Complexes of the bis(phosphine oxide) (213 Z=0) with copper(I) and copper(II), and of the related disulfide (213 Z=S) with gold(I) and silver(I), have been characterised. 

Phosphine Chalcogenides as Ligands.- Spectroscopic evidence has been obtained for the existence of a reversible coordinative interaction between a phosphine oxide (in both the free and metal-coordinated state) and sulphur dioxide. Intramolecular coordinative interactions between the phosphoryl group and both fluoroboron and fluorophosphorane acceptors, e.g., (220), have been established by spectroscopic techniques. The coordination chemistry of... 

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