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
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- 作者：José ; Vicente ; Marí ; a Teresa Chicote ; Pablo Gonzá ; lez-Herrero ; Peter G. Jones ; Mark G. Humphrey ; Marie P. Cifuentes ; Marek Samoc ; and Barry Luther-Davies
- 刊名：Inorganic Chemistry
- 出版年：1999
- 出版时间：November 1, 1999
- 年：1999
- 卷：38
- 期：22
- 页码：5018 - 5026
- 全文大小：120K
- 年卷期：v.38,no.22(November 1, 1999)
- ISSN：1520-510X
文摘
hars/beta2.gif" BORDER=0 ALIGN="middle">-Diketonato complexes [Tl{CH{C(O)R}2}] or PPN[Au{CH{C(O)R}2}2] [where PPN = (Ph3P)2N] react withan excess of CS2 to give, respectively, [Tl2{S2C=C{C(O)R}2}]n [R = Me (1) or Ph (2)] or (PPN)2[Au2{
-hars/kappa.gif" BORDER=0 >2-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 obtainedfrom PPN[AuCl2] and the corresponding thallium 1,1-ethylenedithiolate. PPN[AuCl4] reacts with 1 to givePPN[Au{hars/kappa.gif" BORDER=0 >2-S2C=C{C(O)Me}2}2] (5) which, in turn, reacts with PhICl2, Br2 or I2 (1:1) to give PPN[AuX2{hars/kappa.gif" BORDER=0 >2-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{hars/kappa.gif" BORDER=0 >2-S2C=C{C(O)Me}2}(phen)]CF3SO3 (9) can be obtained. Thecrystal 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 hars/pi.gif" BORDER=0 >-system isobserved, with the anionic dimetallacycle containing two gold and four sulfur atoms in 3 responsible for thelargest nonlinearities (approximately 100 × 10-36 esu).