The Phosphine-Stabilized Gold-Arsenic Clusters [Au19(AsnPr)8(dppe)6]Cl3, [Au10(AsnPr)4(dppe)4]Cl2, [Au17(AsnPr)6(As2nPr2)(dppm)6]Cl3, and [Au10(AsPh)4(dppe)4]Cl2: Synthesis, Characterization, and DFT Calculations

摘要

A limited number of gold-arsenic complexes have been described in the literature, including compounds containing arsenic bridges (for example, [(Ph3PAu)4As]BF4,[1] [Au4(As4Ph4)2(PnPr3)4],[2] and [Au10(AsPh)4(PhAsSiMe3)2(PnPr3)6][2]) or terminal AsR3 ligands (for example, [(Ph3As)xAu]BF4 (x=2, 4),[3] [(Ph3AsAu)3O]BF4,[3] [Au(C6F5){(SPh2)2C(AuAsPh3)2}]ClO4,[4] and [Au4Cl2{Ph2PCH2As(Ph)CH2PPh2}2]X2 (X=PF6, NO3)[5]), as well as [Au16(AsPh3)8Cl6], which contains a centered icosahedron of 13 gold atoms.[6] In contrast, the rich chemistry of gold and gold-chalcogen clusters has been extensively studied.[7]-[10] At first, it seemed that gold clusters preferred icosahedral structures or fragments thereof,[7a], [b], [8d] but a variety of other structural motifs have since been encountered: tetrahedra ([tBu3PAu]4(BF4)2[9c] and [(R3PAu)4O](BF4)2 (R=Ph, o-C6H4Me)[9k]), square pyramids ([(Ph3PAu)5P](BF4)2,[9l]), trigonal bipyramids ([{(Ph3P)6Au5}P](BF4)3[9j]), edge-sharing bi-tetrahedra ([Au6(PPh3)6](NO3)2[8g]), noncentered and centered crowns (K[Au(AuCl)(AuPPh3)8](PF6)2[9n] and [Au9{P(p-C6H4OMe)3}8](BF4)3[8c]), and octahedra ([Au6{P(p-C6H4Me)3}6](BF4)2[7c] and [(Ph3PAu)6C](CH3OBF3)2[8i]).