VARIATIONS IN THE CHAIN STRUCTURE OF CATIONIC (PHOSPHINE)GOLD(I) DIALKYLDITHIOPHOSPHATE COMPLEXES

Treatment of dithiophosphoric acid diesters (RO)(2)P(S)SH with appropr iate quantities of tris[(phosphine)gold(I)]oxonium tetrafluoroborates {[(R-3'P)Au](3) O}(+) BF4- in dichloromethane gives di- or trinuclear complexes of the types {(RO)(2)P[SAu(PR3')](2/3)}(+/2+) (2) BF4- as co lourless, crystalline salts. As determined by single crystal X-ray dif fraction studies, in the 1:2 complexes (with R = R' = Me and R' = Et, R = Ph and o-Tol), each gold atom is attached to a different sulfur at om, but with short intracationic Au-Au contacts. These cations are ass ociated to form strings through intermolecular Au-Au contacts in the f irst case (R = Et), but through additional Au-S contacts in the second (R = Ph). For R = o-Tol, the cations are not associated at all owing to steric hindrance. This result is indicative of very small energy di fferences between the two modes of association. The 1:3 complexes are fluxional in solution and show virtually equivalent R3PAu groups in th e NMR spectra at 20 degrees C, but at low temperature non-equivalent l igands can be distinguished as shown previously for analogous dithioph osphinate derivatives.