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

Abstract

beta-Diketonato complexes [Tl{CH{C(O)R}(2)}] or PPN[Au{CH{C(O)R}(2)}(2)] [where PPN = (Ph(3)P)(2)N] react with an excess of CS(2) to give, respectively, [Tl(2){S(2)C=C{C(O)R}(2)}](n)() [R = Me (1) or Ph (2)] or (PPN)(2)[Au(2){&mgr;-kappa(2)-S(2)C=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[AuCl(2)] and the corresponding thallium 1,1-ethylenedithiolate. PPN[AuCl(4)] reacts with 1 to give PPN[Au{kappa(2)-S(2)C=C{C(O)Me}(2)}(2)] (5) which, in turn, reacts with PhICl(2), Br(2) or I(2) (1:1) to give PPN[AuX(2){kappa(2)-S(2)C=C{C(O)Me}(2)}] [X = Cl (6), Br (7), or I (8)]. By reacting 6 with TlCF(3)SO(3) and 1,10-phenanthroline (phen) in 1:2:1 molar ratio, the cationic complex [Au{kappa(2)-S(2)C=C{C(O)Me}(2)}(phen)]CF(3)SO(3) (9) can be obtained. The crystal structures of 5 and 6.0.5Me(2)CO have been determined. Third-order nonlinearities of 3.PPN, 3.Pr(4)N, 5, and 6 have been evaluated by the Z-scan technique; an increase in nonlinearity upon extending the pi-system is observed, with the anionic dimetallacycle containing two gold and four sulfur atoms in 3 responsible for the largest nonlinearities (approximately 100 x 10(-36) esu).

Experimental and Theoretical Study of Gold(III)-Catalyzed Hydration of Alkynes

“…The Au–S bond length of 2.3005(14) Å in 2 is nearly identical with the mean value of 2.3038 Å found in complexes of the type [AuX 2 (dtc)] (X = Cl, Br), in which the Au–S bond distances vary from 2.287(3) Å in [AuCl 2 {μ-S 2 CN(EtOH) 2 }] to 2.319(2) Å in [AuBr 2 {μ-S 2 CN(Me)(CH 2 CO 2 Et)}] . It also compares well with those observed in the [AuCl 2 (μ-SCS)] − complexes cited above, in which the Au–S distances range from 2.273 Å in NBu 4 [AuCl 2 {μ-S 2 CC(CN)(CO 2 Et)}] to 2.305(3) Å in [AuCl 2 {μ-S 2 CN(EtOH) 2 }] …”

“…The Au–Cl bond length of 2.3116(15) Å is slightly long for a gold(III) complex, which could favor the displacement of the Cl by the corresponding alkyne in the catalytic process ( vide infra ). This is due to the strong trans influence of the S donor ligands and is of the same order as the Au–Cl bond distances found in the related dithiocarbamate complex [AuCl 2 {μ-S 2 CN(EtOH) 2 }] (2.316(3) and 2.325(3) Å) or in other compounds containing the fragment [AuCl 2 (μ-SCS)] − but significantly shorter than in [AuCl 2 {μ-S 2 CC{C(O)Me} 2 }] (2.3491(13)–2.3662(13) Å) …”

“…This is due to the strong trans influence of the S donor ligands and is of the same order as the Au−Cl bond distances found in the related dithiocarbamate complex [AuCl 2 {μ-S 2 CN(EtOH) 2 }] (2.316(3) and 2.325(3) Å) 37 or in other compounds containing the fragment [AuCl 2 (μ-SCS)] 38−40 but significantly shorter than in [AuCl 2 {μ-S 2 CC{C(O)Me} 2 }] (2.3491(13)−2.3662(13) Å). 41 The Au−S bond length of 2.3005( 14) Å in 2 is nearly identical with the mean value of 2.3038 Å found in complexes of the type [AuX 2 (dtc)] (X = Cl, Br), in which the Au−S bond distances vary from 2.287 42 It also compares well with those observed in the [AuCl 2 (μ-SCS)] 37−41 complexes cited above, in which the Au−S distances range from 37 Finally, the angles around the central C atom of the dibenzyldithiocarbamate ligand in compound 2 (see Figure 1) are consistent with sp 2 hybridization, although the S−C−S angle (109.6(4)°) is narrower than that expected for this hybridization because of the behavior of the ligand as chelate. A comparison of both types of C−N bond lengths (C(1)−N 1.299(10) Å, C(2)−N 1.491(7) Å) is in accordance with a certain double-bond character in the former.…”

Synthesis, characterization and in vitro cytotoxicity of gold(iii) dialkyl/diaryldithiocarbamato complexes

“…The S 1 -Au 1 -S 2 , and S 2 -Au 1 -S It also compares well with those observed in the [AuCl 2 (m-SCS)] complexes. [49][50][51][52] 3.4. In vitro cytotoxicity Normal human foetal lung cells (MRC5) and three different human cancer cell lines including breast (MCF7) and ovarian (A2780, A2780R) were used as experimental models for evaluation of in vitro cytotoxicity of the prepared complexes 1-6, see Table 3.…”

Doped and low-alloyed gold bonding wires

“…These gold alloys usually contain up to 1% alloying elements, in some cases up to 5% (14,15). The most important alloying elements are the precious metals Ag, Pd, Pt, and also Cu (10, 16 -18).…”