Synthesis and characterization of dinuclear gold(I) ring and open-ring complexes containing saturated and unsaturated dithiol bridging ligands and phosphine or bis(diphosphine) donor ligands. Crystal structures of [Au2(.mu.-S(CH2)3S) (.mu.-dppm)], [Au2(.mu.-MNT)(PPh3)2], [Au2(.mu.-S2C6H4) (PPh3)2], and [Au4(.mu.-S2C6H3CH3)2(PEt3)2]

Abstract

Dinuclear gold(1) complexes of the type [Au2(p-dithiolate)(L)J where L is a phosphine or bis(dialky1phosphine) have been synthesized. The molecular structures of [Au2(p-S(CH2)3S)(p-dppm)] [dppm = bis((diphenylphosphin0)-methane)] (l), [Au&MNT)(PPh3)2] (MNT = 1 ,Zdicyanoethene-1,2-dithiolate-S,S? (2), and [Au2(p-S2C6H4)-(PPh3)2] (3) aredescribed. In addition, the structure ofthe tetranuclear bis(dithio1ate) [ A u~(~( -S~C~H~C H & ( P E~~)~] (4) is reported. Compound 1 exhibits linear S-Au-P coordination and significant metal-metal interaction, Au-Au= 3.128( 1) A. The open-ring complexes 2 and 3contain an irregular three-coordinate gold(1) center and a "normal" two-coordinate, linear gold(1) center in contrast to 1. Compound 4 is a result of [Au(PEt3)]+ coordination to [Au2(pc-S&H3CH3)2l2-. Pertinent crystal data are as follows: Compound 1 crystallized in the monoclinic space group C 2 / c with a = 29.765(9) A, b = 11.479(2) A, c = 18.032(4) A, B = 114.65(1)', and V = 5600(2) A3. Compound 2.Et20 crystallized in the space group P2l/c with a = 17.663(5) A, b = 14.185(3) A, c = 18.780(3) A, j3 = 114.853(18)', and V = 4269(2) A3. Compound 3 crystallized in the space group P21 with 4 = 10.761(4) A, b = 10.687(4) A, c = 16.227(5) A, j3 = 98.82(3)O, and V = 1844(1) A3. Compound 4 crystallized in the space group P21 with a = 9.767(2) A, b = 12.373(3) A, c = 14.096(3) A, j3 = 92.71(2)O, and V = 1707(1) A3.

Application of 2,6-Diphenylpyridine as a Tridentate [C∧N∧C] Dianionic Ligand in Organogold(III) Chemistry. Structural and Spectroscopic Properties of Mono- and Binuclear Transmetalated Gold(III) Complexes

“…This is attributed to the tethered nature of the phenyl substituents with respect to the pyridine ring, which evidently restricts the bite angle. The gold−sulfur bond length of 2.296(2) Å in 3 is very similar to those in the gold(I) complexes Au(8-S-quinoline)(PPh 3 ) (2.296(8) Å) and [Au 2 (μ-S(CH 2 ) 3 S)(μ-dppm)] (2.281(4) and 2.288(3) Å) . In 4 , the Au(1)−P(1) distance (2.283(1) Å) resembles that in [AuCl{2-(2-pyridylmethyl)phenyl}(PPh 3 )]BF 4 (2.311(3) Å) 9a.…”

The Chemistry of Gold

“…These contain a diphosphine in addition to other bidentate ligands such as bis(ylide) [135,136], dithiolate [137], dithiocarbamate [136,138], xantate [139], phosphoniodithioformate [140], dithiophosphinate [141], pyridine-2thiolate [136], and so on. These contain a diphosphine in addition to other bidentate ligands such as bis(ylide) [135,136], dithiolate [137], dithiocarbamate [136,138], xantate [139], phosphoniodithioformate [140], dithiophosphinate [141], pyridine-2thiolate [136], and so on.…”

“…As a consequence of these aurophilic interactions, many of these complexes present luminescence properties. Substituted phenylene-dithiolate ligands have been thoroughly studied and di-, tri-and tetranuclear complexes of the type [Au 2 (m-S 2 C 6 H 3 R)(PPh 3 ) 2 ], [Au 3 (m-S 2 C 6 H 3 R)(PPh 3 ) 3 ] þ or [Au 4 (S 2 C 6 H 3 R) 2 L 2 ] have been reported with the ortho isomer [137,153,[164][165][166]. A chiral luminescent Au 16 ring has been reported by reaction of [Au 2 Cl 2 (m-dppm)] with K 2 (pippzdc) (pippzdc ¼ piperazine-1,4-dicarbodithiolate) which gives the tetramer [Au 4 (pippzdc)(dppm) 2 ] 4 [160].…”

Crystal structure of bis(3,5-dimethylpyrazole)-N,N'-µ-[1-bis(diphenylphosphino) propane]-P,P'-digold(I)] diperchlorate, C37H42N4P2AU2CI2O8

“…In these complexes the ligands opposite to the coordinated Ρ atom can be alogenides [2][3][4][5] or anionic species containing Ν [6,7], C [8], Ο [9], or S [10,11] as donor atoms. Their structures show that intra or intermolecular gold-gold interactions might be present.…”