TY - JOUR
T1 - Gold(I)-Clustering at a Primary Arylphosphine with Bulky Substituents
T2 - [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
AU - Zeller, Edgar
AU - Beruda, Holger
AU - Riede, Jürgen
AU - Schmidbaur, Hubert
PY - 1993
Y1 - 1993
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0001584222&partnerID=8YFLogxK
U2 - 10.1021/ic00066a017
DO - 10.1021/ic00066a017
M3 - Article
AN - SCOPUS:0001584222
SN - 0020-1669
VL - 32
SP - 3068
EP - 3071
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 14
ER -