Heterocyclic Mercaptan - Synthesis, Structure And Reaction Properties Of Transition Metal Compounds

The synthesis and properties of heterocyclic thione- transition metal compounds are in the first place for coordination chemistry. The use of ctransition metal complexes has been directed toward broadening of their application in optic, electronic and magnetic chemistry, catalysis and in the pharmaceutical industry.This dissertation describes the synthesis and structural characterization of heterocyclic thione-transition metal complexes, which have being placed in two fields. One is the synthesis of those half-sandwich complexes containing heterocyclic thione ligands; the other is the synthesis of pyridine-4-thionate Palladium complexes.In this dissertation, seventeen complexes were successfully synthesized, and five of them were determined through X-ray single crystal diffraction analysis.This dissertation consists of listed contents:(1) The reactions of Cp^*CoI₂(CO) with lithium benzo[d]thiazole-2-thiolate, lithium benzo[d]oxazole-2-thiolate and lithium thiazoline-2-thiolate yields a newη²-N, S coordination family of half-sandwich cobalt complexes, Cp^*CoI(2-BtaS) (1), Cp^*CoI(2-BoaS) (2) and Cp^*CoI(2-TaS) (3), [Cp^* = pentamethylcyclopentadienyl, 2-BtaS = benzo[d]thiazole-2-thiolate, 2-BoaS = benzo[d]oxazole-2-thiolate, 2-TaS = thiazoline-2-thiolate] respectively. In the same way, the treatment of Cp^*CoI₂(CO) and CpCoI₂(CO) with lithium 4-pyridinethiolate and 4-LiS-C₆H₄-N=CH-4'-C₅H₄N (LiL) affords unexpected dinuclear disulfide complexes (Cp^*CoI₂)₂(4-PDS) (4), (CpCoI₂)₂(4-PDS) (5) and (Cp^*CoI₂)₂(L-L) (6) [Cp = cyclopentadienyl, 4-PDS = 4,4'-dipyridyldisulfide]. The molecular structure of 5 has been determined by X-ray crystallographic analysis.(2) Two novel neutral triangular metallomacrocycles, [Cp^*RhCl(μ-4-PyS)]₃ (7) and [Cp^*IrCl(μ-4-PyS)]₃ (8) [4-PyS = 4-pyridinethiolate], have been synthesized by self-assembly reactions of [Cp^*RhCl₂]₂ and [Cp^*IrCl₂]₂ with lithium 4-pyridinethiolate, respectively. In situ reaction of complex 7 with 3 equivalent of lithium 4-pyridinethiolate resulted in [Cp^*Rh(μ-4-PyS)(4-PyS)]₃ (9) containing both skeleton and pendent 4-PyS groups. Chelating coordination mode of 2-pyridinethiolate broke down the triangular skeleton to give mononuclear metalloligands Cp^*Rh(2-PyS)(4-PyS) (10) and Cp^*Ir(2-PyS)(4-PyS) (11) [2-PyS = 2-pyridinethiolate], which could also be synthesized from Cp^*RhCl(2-PyS) and Cp^*IrCl(2-PyS) with lithium 4-pyridinethiolate. The coordination reactions of 10 with [Cp^*RhCl₂]₂ and [Cp^*IrCl₂]₂ gave dinuclear complexes [Cp^*Rh(2-PyS)(μ-4-PyS)][Cp^*RhCl₂] (12) and [Cp^*Rh(2-PyS)(μ-4-PyS)][Cp^*IrCl₂] (13), respectively. Molecular structures of 7, 8 and 10 were determined by X-ray crystallographic analysis.(3) Three neutral triangular metallomacrocycles, [Ph₃PPdCl(μ-4-PyS)]₃ (14), [Cy₃PPdCl(μ-4-PyS)]₃ (15) and [PhO₃PPdCl(μ-4-PyS)]₃ (16), have been synthesized by reactions of [Ph₃PPdCl₂]₂, [Cy₃PPdCl₂]₂ and [(PhO)₃PPdCl₂]₂ with lithium 4-pyridinethiolate, respectively. Treatment of (Ph₃P)₂PdCl₂ with lithium 4-pyridinethiolate result in mononuclear complex (Ph₃P)₂PdCl(4-PyS) (17). Complex 14,15 and 17 catalyzes the Suzuki-Miyaura cross-coupling reactions of aryl bromides with phenylboronic acid in moderate yields.