98875-33-3Relevant academic research and scientific papers
Reactivity of 16- and 18-electron mixed platinum-gold clusters with halides. Crystal and molecular structures of [Pt(PPh3)(AuPPh3)6(AuCl) 3]·2C4H10O
Schoondergang,Bour,Van Strijdonck,Schlebos,Bosman,Smits,Beurskens,Steggerda
, p. 2048 - 2052 (2008/10/08)
In the reaction of the 16-electron cluster [Pt(AuPPh3)8](NO3)2 with X (X = I, SCN, Cl) [Pt(PPh3)(AuPPh3)6(AuX)3] is formed in about 40% yield. The crystal and molecular structures of [Pt(PPh3)(AuPPh3)6(AuCl) 3]·2C4H10O have been investigated by X-ray analysis (monoclinic, space group P21/n, a = 15 938 (4) A?, b = 52.764 (14) A?, c = 16.747 (4) A?, β = 105.06 (3)°, V = 13 600 A?3, Z = 4, Cu Kα radiation). The residuals are R = 0.060 and Rw = 0.068 for 8243 observed reflections and 466 variables. The symmetry of the metal cluster is C3v. In the metal cluster the central Pt atom is surrounded by six AuPPh3 groups, three AuCl groups, and one phosphine. The reaction of the 18-electron systems [Pt(CO)(AuPPh3)8](NO3)2 and [Pt(H)(PPh3)(AuPPh3)7](NO3) 2 with NBu4+ halides leads to the substitution of one Au-bonded PPh3 and the formation of respectively [Pt(CO)(AuPPh3)7(AuX)]+ and [Pt(H)(PPh3)(AuPPh3)6(AuX)]+ (X = Cl, Br, I) The products are characterized by elemental analysis and 31P, 195Pt, and 13C NMR spectroscopy and are discussed in terms of the electronegativity of the ligand X. The reactions of [Pt(H)(AuPPh3)8]+ and [Pt(CO)(Ag)(AuPPh3)8]3+ with Cl , Br , or I- lead to a decomposition of the clusters.
X-ray crystal structure and31P NMR solution studies of [Ir2(dimen)4(PPh3)Au(PPh3)](PF 6)3 (dimen = 1,8-diisocyano-p-menthane). Observation of partial site preference in the formation of "outside" Ag and Au adducts
Sykes, Andrew G.,Mann, Kent R.
, p. 7247 - 7254 (2007/10/02)
The reaction of [M(PPh3)2](PF6) (M = Ag, Au) with [Ir2(dimen)4](PF6)2 leads to the formation of heteronuclear complexes of the general formula [Ir2(dimen)4(PPh3)M(PPh3)](PF 6)3. Recrystallization of the Au complex from CH3CN/ether solution afforded crystals of [Ir2(dimen)4(PPh3)Au(PPh3)](PF 6)3-CH3CN (AuIr2C86H105F18N9P 5) that were the subject of an X-ray crystal structure characterization. The complex crystallizes in the monoclinic space group Cc (No. 9) with Z = 4; a = 24.79 (2), b = 15.792 (6), c = 23.307 (6) ?; β = 94.15 (4)°; V = 9102 A°3. At convergence, R = 0.055 and Rw = 0.064 for 6382 observed reflections. The crystal contains tripositive cations with a Au(PPh3)+ unit occupying one of the [Ir2(dimen)4]2+ axial sites and a PPh3 in the second axial position. The PPH3-Ir2-Au(PPh3) moiety features a two-electron two-center Ir-Au bond with a Ir-Au distance of 2.607 (2) ?. Au-P and Ir-P bond distances in the structure are 2.199 (7) and 2.482 (7) ?, respectively. The Ir(CNR)4 planes are nearly staggered with a twist angle of 39°. The Ir-Ir separation is 2.986 (2) ?. From 31P{1H} NMR solution studies and homonuclear 31P{1H} δ/J-resolved NMR spectroscopy, a nonstatistical distribution of five out of six different geometric isomers is present in CH2Cl2 solutions of both the Ag+ and Au+ complexes.
