Gold® phosphine

Schwerdtfeger, P., Hermann, H.L. and Schmidbaur, H. (2003) The Stability of the Gold - Phosphine Bond. A Comparison with other Group 11 Elements. Inorganic Chemistry, 42, 1334—1342. 

Malik, N.A., Otiko, G. and Sadler, P.J. (1980) Control of intra- and extra-cellular sulfhydryl-disulfide balances with gold phosphine drugs Phosphorus-31 nuclear magnetic resonance studies of human blood. Journal of Inorganic Biochemistry, 12, 317-322. 

Hydroamination of olefins has received considerable attention this year as a route to functionalized piperidines and spiropiperidines, particularly in regard to the investigation of new catalysts. In the synthesis of spiro-piperidines, two new mild and more general intramolecular hydroamination protocols were developed this year. One protocol uses a cationic gold-phosphine complex (Au[P(fBu)2(o-biphenyl)]Cl) as the catalyst... 

Two gold-phosphine units can bridge opposite Ru-Ru edges of the equatorial plane [318, 395], as in [(Ph3P)Au]2Ru6(p,6-C)(CO)i6 269 [318], or non-adjcent Ru-Pt... 

The yields of these reactions are often improved by the addition of thallium(I) or silver(I) salts to act as halide scavengers and so generate the gold phosphine fragment in situ. This modification has been most extensively utilized in the addition of Au(PR3)+ to anionic and neutral cluster compounds, and a number of examples are given below ... 

Other reagents that have been used as sources of the gold phosphine fragment include [Au(PMe2Ph)2]+ (79,192) and [(AuPPh3)30] + ... 

In the reactions described above, only the AuPR3 fragment of the gold phosphine precursor has added to the cluster. Oxidative addition of Au(PR3)X [where X = Cl (90,188, 191), Br (90, 188), I (179), SCN (104), NCO (231), C2R (92, 97), etc.] has also been observed to occur, yielding clusters in which the transition metal is in a higher oxidation state. This type of reaction was first investigated by Nyholm and coworkers (90, 232), and some examples are given below ... 

The addition of gold phosphine fragments to transition metal compounds is readily extended to include reactions of heteronuclear gold cluster compounds and has been used to build up clusters of increasing nuclearity, as the following examples illustrate ... 

In contrast to the above reactions, a gold phosphine fragment can often be readily removed from a heterometallic cluster by the addition of free phosphine. This can result in degradation to novel heterometallic clusters containing fewer gold atoms,... 

The gold phosphine fragment has also been abstracted from heteronuclear cluster compounds as Au(PR3)X by reaction with halide ions... 

The gold phosphine fragment has been used extensively as a cluster building unit and numerous examples of AuPR3 groups bridging metal-metal bonds have been structurally characterized, in which the gold moieties exhibit /i,2- and -coordination modes. Tables V and VI... 

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