Complexes with S-Donor Ligands. 7. New 1,1-Ethylenedithiolato Complexes of Thallium(I), Gold(I), and Gold(III): Syntheses, Structure, and Molecular Cubic Hyperpolarizabilities^†

β-Diketonato complexes [Tl{CH{C(O)R}2}] or PPN[Au{CH{C(O)R}2}2] [where PPN = (Ph3P)2N] react with an excess of CS2 to give, respectively, [Tl2{S2CC{C(O)R}2}]n [R = Me (1) or Ph (2)] or (PPN)2[Au2{μ-κ2-S2CC{C(O)R}2}2] [R = Me (3·PPN) or Ph (4·PPN)]. The gold complexes 3·PPN and 4·PPN can also be obtained from PPN[AuCl2] and the corresponding thallium 1,1-ethylenedithiolate. PPN[AuCl4] reacts with 1 to give PPN[Au{κ2-S2CC{C(O)Me}2}2] (5) which, in turn, reacts with PhICl2, Br2 or I2 (1:1) to give PPN[AuX2{κ2-S2CC{C(O)Me}2}] [X = Cl (6), Br (7), or I (8)]. By reacting 6 with TlCF3SO3 and 1,10-phenanthroline (phen) in 1:2:1 molar ratio, the cationic complex [Au{κ2-S2CC{C(O)Me}2}(phen)]CF3SO3 (9) can be obtained. The crystal structures of 5 and 6·0.5Me2CO have been determined. Third-order nonlinearities of 3·PPN, 3·Pr4N, 5, and 6 have been evaluated by the Z-scan technique; an increase in nonlinearity upon extending the π-system is observed, with the anionic dimetallacycle containing two gold and four sulfur atoms in 3 responsible for the largest nonlinearities (approximately 100 × 10-36 esu).β-二酮合配合物[β-Diketonato complexes] [Tl{CH{C(O)R}2}] 或 双(三苯基膦)亚胺（PPN，(Ph3P)2N）[Au{CH{C(O)R}2}2] 与过量二硫化碳（CS2）反应，分别生成[Tl2{S2C=C{C(O)R}2}]n [R=甲基（Me，1）或苯基（Ph，2）] 或 (PPN)2[Au2{μ-κ2-S2C=C{C(O)R}2}2] [R=甲基（3·PPN）或苯基（4·PPN）]。金配合物3·PPN与4·PPN也可通过PPN[AuCl2]与相应的铊基1,1-乙二硫醇盐反应制得。PPN[AuCl4]与1反应生成PPN[Au{κ2-S2C=C{C(O)Me}2}2]（5），该产物进一步与PhICl2、Br2或I2按1:1的摩尔比反应，得到PPN[AuX2{κ2-S2C=C{C(O)Me}2}] [X=氯（Cl，6）、溴（Br，7）或碘（I，8）]。将6与三氟甲磺酸铊（TlCF3SO3）和1,10-邻菲啰啉（phen）按1:2:1的摩尔比反应，可得到阳离子配合物[Au{κ2-S2C=C{C(O)Me}2}(phen)]CF3SO3（9）。已解析出配合物5和6·0.5丙酮（Me2CO）的晶体结构。采用Z扫描（Z-scan）技术评估了3·PPN、3·四丙基铵（Pr4N）、5和6的三阶非线性光学性能；研究发现随着π共轭体系的扩展，非线性光学效应增强，其中含两个金原子与四个硫原子的阴离子双金属环化合物3展现出最大的非线性光学响应（约100×10^-36 esu，静电单位（electrostatic unit））。