Polynuclear ((diphenylphosphino)methyl)phenylarsine bridged complexes of gold(I). Bent chains of gold(I) and a role for Au(I)-Au(I) interactions in guiding a reaction

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

“…A limited number of gold-arsenic complexes have been described in the literature, including compounds containing arsenic bridges (for example, [(Ph 3 PAu) 4 As]BF 4 , [1] [Au 4 -(As 4 Ph 4 ) 2 (PnPr 3 ) 4 ], [2] and [Au 10 (AsPh) 4 (PhAsSiMe 3 ) 2 -(PnPr 3 ) 6 ] [2] ) or terminal AsR 3 ligands (for example, [(Ph 3 As) x Au]BF 4 (x = 2, 4), [3] [(Ph 3 AsAu) 3 O]BF 4 , [3] [Au-(C 6 F 5 ){(SPh 2 ) 2 C(AuAsPh 3 ) 2 }]ClO 4 , [4] and [Au 4 Cl 2 {Ph 2 PCH 2 -As(Ph)CH 2 PPh 2 } 2 ]X 2 (X = PF 6 , NO 3 ) [5] ), as well as [Au 16 -(AsPh 3 ) 8 Cl 6 ], which contains a centered icosahedron of 13 gold atoms. [6] In contrast, the rich chemistry of gold and goldchalcogen clusters has been extensively studied.…”

“…[6] In contrast, the rich chemistry of gold and goldchalcogen clusters has been extensively studied. [7][8][9][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 ([tBu 3 PAu] 4 -(BF 4 ) 2 [9c] and [(R 3 PAu) 4 O](BF 4 ) 2 (R = Ph, o-C 6 H 4 Me) [9k] ), square pyramids ([(Ph 3 PAu) 5 and [Au 9 {P(p-C 6 H 4 OMe) 3 and [(Ph 3 PAu) 6 C](CH 3 OBF 3 ) 2 [8i] ). Herein, we report the synthesis and properties of the new compounds 1-4 obtained from reactions of gold(i) phosphine complexes with As(R)(SiMe 3 ) 2 (R = nPr, Ph; Scheme 1).…”

“…A more detailed analysis is necessary to discriminate between the alternatives. If the shorter bonds are considered ( Table 2, entries [4][5][6][7][8][9][10][11][12][13][14], it is apparent that the lengths calculated for 1 a are slightly greater than the experimental lengths, the deviations being in the usual range (less than 6 pm). The same holds for 1 b and 1 c, with the exception that the values in [a] The atomic numbering refers to Figure 1.…”

Polymorphism and luminescent behavior of linear, two-coordinate gold(i) complexes

“…In cases where multiple Au ... Au interactions can occur, aurophilic attractions between molecules can persist in solution even when other conventional donors are present (22,23).…”

Die phosphanstabilisierten Gold‐Arsen‐Cluster [Au19(AsnPr)8(dppe)6]Cl3, [Au10(AsnPr)4(dppe)4]Cl2, [Au17(AsnPr)6(As2nPr2)(dppm)6]Cl3 und [Au10(AsPh)4(dppe)4]Cl2 – Synthese, Charakterisierung und DFT‐Rechnungen

“…In der Literatur finden sich nur wenige Gold-Arsen-Komplexe: Beschrieben wurden beispielsweise Verbindungen mit Arsenbrücken -[(Ph 3 PAu) 4 As]BF 4 , [1] [Au 4 (As 4 Ph 4 ) 2 -(PnPr 3 ) 4 ] [2] oder [Au 10 (AsPh) 4 (PhAsSiMe 3 ) 2 (PnPr 3 ) 6 ] [2] -, solche mit terminalen AsR 3 -Liganden -[(Ph 3 As) x Au]BF 4 (x = 2, 4), [3] [{(Ph 3 As)Au 3 }O]BF 4 , [3] [Au(C 6 F 5 ){(SPh 2 ) 2 C-(AuAsPh 3 ) 2 }]ClO 4 [4] oder [Au 4 Cl 2 {Ph 2 PCH 2 As(Ph)CH 2 -PPh 2 } 2 ]X 2 (X = PF 6 , NO 3 ) [5] -sowie [Au 16 (AsPh 3 ) 8 Cl 6 ] mit einem zentrierten Ikosaeder aus 13 Goldatomen. [6] Dem gegenüber stehen umfangreiche Arbeiten zur Chemie der Goldund Goldchalkogen-Cluster.…”