Gold(I)-Clustering at a Primary Arylphosphine with Bulky Substituents: [2,4,6-(Me3C)3C6H2P(AuPR3)n](n−2)+ (R = t−Bu, Ph; n = 2−4) Complexes and Crystal Structure of the Species with n = 3 and R = Ph

Edgar Zeller, Holger Beruda, Jürgen Riede, Hubert Schmidbaur

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Abstract

Reaction of the primary phosphine ArPH2 (Ar = 2,4,6-(Me3C)3C6H2) with [O(AuL)3]+BF4 reagents yields the trinuclear gold complexes [ArP(AuL)3]+BF4 (1, L = PPh3; 2, L = P-t-Bu3). A further equivalent of Ph3PAu+BF4 can be added to 1 to give [ArP(AuPPh3)4]2+(BF4−)2 (3), whereas for 2 the analogous reaction leads to decomposition and formation of [(t-Bu3P)2Au]+BF4. The neutral intermediate [ArP(AuP-t-Bu3)2] (4) can be obtained in a mixture with 2 upon treatment of ArPH2 with the corresponding oxonium reagent in a molar ratio of 3:2. All products are colorless air-stable solids, which have been characterized by analytical and spectroscopic data, including an X-ray crystal structure analysis for complex 1. Crystals of 1·2CH2Cl2 from CH2Cl2/diethyl ether are triclinic, P1̅, with a = 13.520(1) Å,b= 13.901(1) Å, c = 20.346(2) Å, 1 = 85.57(1)°, β = 87.23(1)°, γ = 87.23(1)°, V = 3678.2 Å3, dcalc = 1.73 g/cm3, and Z = 2. In the cations of 1, the phosphorus atom is attached to a single gold atom on one side of the ArP plane and to a pair of gold atoms on the other. Clearly, the two ortho t-Bu groups separate the gold atom triad, which is known to form a triangle in the absence of steric hindrance. In solution, rapid site exchange renders the LAu units NMR-equivalent. A symmetrical structure with two Au2 pairs at the pentacoordinate phosphorus atom is assigned to complex 3, while for 4 the digold(I) arylphosphide stoichiometry indicates a three-coordinate phosphorus atom.

Original languageEnglish
Pages (from-to)3068-3071
Number of pages4
JournalInorganic Chemistry
Volume32
Issue number14
DOIs
StatePublished - 1993
Externally publishedYes

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