| The synthesis and properties of chalcogen half-sandwich transition metal compounds are in the first place for organometallic chemistry. The use of chalcogen half-sandwich transition metal complexes has been directed toward broadening of their application in desulfurization and hydrogenation study, semiconductor, nonlinear optic materials, energy storage and so on.This dissertation describes the synthesis and structural characterization of chalcogen half-sandwich transition metal organometallic complexes, which have being placed in two fields. One is the synthesis of those half-sandwich complexes containing pyridinethiolate ligands; the other is the synthesis of dithiolato carborane half-sandwich complexes containing functionalized cyclopentadienyl ligands.In this dissertation, fourteen complexes were successfully synthesized, and eight of them were determined through X-ray single crystal diffraction analysis.This dissertation consists of listed contents:(1) The half-sandwich iridium complex Cp*Ir(2-PyS)CI (1) was synthesized by the reaction of [Cp*IrCl2]2 with lithium 2-pyridinethiolate. Other four half-sandwich cobalt complexes, Cp*Co(2-PyS)2 (2), Cp*Co(2-PyS)2·HI (3), Cp*Co(2-PyS) (4-PyS) (4), (Cp*Co)2(μ-PhS)2(μ-2-PyS)I (5) [Cp* = pentamethylcyclopentadienyl, 2-PyS = 2-pyridinethiolate ligand, 4-PyS = 4-pyridinethiolate ligand, PhS = benzenethiolate ligand] were successfully obtained by the reactions of 2-pyridinethiolate, 2-pyridinethione, lithium 4-pyridinethiolate and lithium benzenethiolate with Cp*Co(2-PyS)I, respectively. 2 and 3 have the structures with two 2-pyridinethiolates ligands which coordinated to the cobalt atom by different modes, respectively. Two different pyridinethiolate ligands with different coordination modes can be identified in complex 4. The molecular structure of 5 consists of two Cp*-Co fragments, which are triply bridged by three sulfur atoms from different ligands. The molecular structures of 1,3 and 5 were determined by X-ray crystallographic analysis.(2) Five binuclear half-sandwich cobalt complexes, [(η5-C5H4)Co(CO)I2]2SiMe2 (8), [(η5-C5H4)Co(S2C2B10H10)]2SiMe2 (9), [(η5-C5H4)]2Co2(μ2-S2C2B10H10)SiMe2 (10), [(η5-C5H3)CoI2](μ-I)[(η5-C5H3)Co(CO)I](SiMe2)2 (13), [(η5-C5H3)Co(S2C2B10H10)]2(SiMe2)2 (14), were successfully synthesized in moderate yield by the reactions of corresponding ligands, (C5H5)2SiMe2 (6) and (C5H4)2(SiMe2)2 (11), respectively. The molecular structures of 8, 10, 11, 13 and 14 was determined by X-ray crystallographic analysis, which distinctly depict various molecular structures containing the Cp rings and the metal centers with halide or 1,2-dicarba-closo-dodecaborane-1,2-dithiolato ligands. For the (η5-C5H4)2SiMe2 complexes, coordination of the fragments CpCo favors a exo conformation. With the rigid structure of the bridged ligand (C5H4)2(SiMe2)2, only cis isomers of the corresponding (η5-C5H3)2(Si2Me2)2 complexes are formed. |
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