ISSN:
0009-2940
Keywords:
Gold
;
Gold(I) complexes
;
Phosphinite complexes
;
Phosphite complexes
;
Configuration determination
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The reaction of compounds (R3P) AuMe with diphenylphosphinous acid Ph2P(O)H affords methane and neutral complexes of the type (R3P(O)Ph2 (1a: R = Me; 1b: R = Ph, lc: R = o-Tol). 1a, b are obtained in high yield, but the yield of lc is lower owing to a side-reaction which leads to a different product: Ph2P(OH)-Au-P(O)Ph2 (2). The crystal structure of 1a was determined by a single-crystal X-ray diffraction study. The compounds is a monomer with a linear P-Au-P′ axis and the phosphane and phosphinite ligands in a staggered conformation. In solution (CHCl3, CH2Cl 2/) compounds 1a-c undergo a ligand redistribution, establishing equilibria that involve ionic isomers of the type [R3P)2Au]+ [Au-(P(O)Ph2)2]-, which are readily identified through their NMR data. The analogous reaction of (R3P)b AuMe with dimethylphosphite (MeO)2P(O)H gives methane and the corresponding dimethylphosphites of the type (R3P)AuP(O)(OMe)2 (3a: R = Me; 3b: R = Ph; 3c: R= o-Tol). The crystal structure of 3b has also been determined. It features a linear structure with an eclipsed conformation of the ligands. In polar solvents (CHCl3, methanol) there is again an eqilibrium between neutral and ionic isomers, the latter comprising bis(phosphane)gold cations [(R3P)2Au]+ and {Au[P(O)-(OMe)2]2)- anions, as confirmed by NMR spectroscopy and mass spectrometry.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19971300925
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