F. A. Vollenbroek

Reactions of gold–phosphine cluster compounds. Preparation and X-ray structure determination of octakis(triphenylphosphine)octa-gold bis(hexafluorophosphate)

[Au9L8]3+(L = PPh3) reacts with L to form [Au8L8]2+ and [AuL2]+; preliminary X-ray structural results are reported for [Au8L8][PF6]2.2CH2Cl2(1).

Preparation and X-ray structure determination of [pentakis{1,3-bis(diphenylphosphino)propane}] undecagoldtris(thiocyanate), [Au11{PPh2C3H6PPh2}5](SCN)3

The reaction of Au11[P(p-ClC6H4)3]7(SCN)3 with 1,3-bis(diphenylphosphino) propane (dppp) in methylene chloride leads to the formation of [Au11(dppp)5] (SCN)3 by a total substitution of the ligands. The compound crystallizes in the triclinic space groupP¯1,a=17.369,b=18.222,c=27.810 Å, α=104.00,β=105.25, γ=85.47°,Z=2. The structure was determined by a combination of Patterson, DIRDIF, and Fourier methods, with diffractometer data and refined by least-squares group refinement toR=0.081 for 2774 reflections.

Reactions of gold–phosphine cluster compounds

[Au9L8]3+(L = PPh3) reacts with L to give [Au9L10]3+ and with X–(X = Cl, Br, I, CN, or SCN) to give Au9L8X3 which converts into [Au11L8X2]+ in solution (investigated for X = Cl and SCN); from 31P [1H] n.m.r., i.r., and Mossbauer spectra it is concluded that these new Au9 and Au11 clusters are structurally related to the known complexes [Au9L8]3+ and Au11L7X3, respectively.

X-ray analysis of octakis(tri-p-tolylphosphine) enneagoldtris(hexafluorophosphate), [Au9{P(p-MeC6H4)3}8](PF6)3: A redetermination

A redetermination of the crystal structure of the gold cluster [Au9{P(p-MeC6H4)3}8](PF6)3 has been performed. The compound crystallizes in the tetragonal space group P¯4n2, witha=20.283,c=20.330 Å, andZ=2. The structure was determined by a combination of Patterson and Fourier methods, with diffractometer data, and refined by least-squares methods toR=0.065 for 2435 reflections.

Synthesis of a new pentanuclear gold cluster by metal evaporation. Preparation and X-ray structure determination of [tris{bis(diphenylphosphino)methane}][bis(diphenylphosphino)methanido]pentagold dinitrate

The evaporation of metallic gold into an ethanolic solution of bis(diphenylphosphino)methane (dppmH) and NH4NO3 results in the formation of [Au5(dppmH)3(dppm)](NO3)2 with (dppm)=[Ph2PCHPPh2]–; X-ray structure analysis reveals the presence of an Au–C bond.