title: 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).
authors.affiliation: Australian Photonics Cooperative Research Centre, Laser Physics Centre, Research School of Physical Sciences and Engineering, Australian National University, Canberra, ACT 0200, Australia.
authors.forename: José
authors.initials: J
authors.lastname: Vicente
authors.forename: María Teresa
authors.initials: MT
authors.lastname: Chicote
authors.forename: Pablo
authors.initials: P
authors.lastname: González-Herrero
authors.forename: Peter G.
authors.initials: PG
authors.lastname: Jones
authors.forename: Mark G.
authors.initials: MG
authors.lastname: Humphrey
authors.forename: Marie P.
authors.initials: MP
authors.lastname: Cifuentes
authors.forename: Marek
authors.initials: M
authors.lastname: Samoc
authors.forename: Barry
authors.initials: B
authors.lastname: Luther-Davies