Preparation and properties of cyclopentadienyl- and pentamethylcyclopentadienyl-titanium(IV) complexes with the C8H4S8 ligand, electrical conductivities of their oxidized species, and x-ray crystal structure of Ti(C5Me5)(2)(C8H4S8)

摘要

Ti(C5H5)(2)(C8H4S8) (1), Ti(C5Me5)(2)(C8H4S8)(2). [NMe4][Ti(C5H5)(C8H4S8)(2)] (3), and [NMe4][Ti(C5Me5)(C8H4S8)(2)] (4) [C8H4S82- = 2-{(4,5-ethylenedithio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithiolat e(2-)] were prepared by reaction of Ti(C5H5)(2)Cl-2, Ti(C5Me5)(2)Cl-2, Ti(C5H5)Cl-3, or Ti(C5Me5)Cl-3 with Li2C8H4S8 or [NMe4](2)[C8H4S8] in THF. They were oxidized by iodine, the ferrocenium cation, or TCNQ (7,7,8,8-tetracyano-p-quinddimethane) in CH2Cl2 or in acetone to afford one-electron-oxidized and over-one-electron-oxidized species, [Ti(C5H5)(2)(C8H4S8)]. I-3, [Ti(C5H5)(2)(C8H4S8)][PF6], [Ti(C5Me5)(2)(C8H4S8)].I-3, [Ti(C5Me5)(2)(C8H4S8)][PF6], [Ti(C5H5)(C8H4S8)(2)].I-0.9, [Ti(C5H5)(C8H4S8)(2)] [TCNQ](0.3), [Ti(C5Me5)(C8H4S8)(2)].I-2.4, and [Ti(C5Me5)(2)(C8H4S8)(2)][TCNQ](0.3), with the C8H4S8 ligand-centered oxidation. They exhibited electrical conductivities of 1.6 x 10(-1) to 7.6 x 10(-4) S cm(-1) measured for compacted pellets at room temperature. The crystal structure of 2 was clarified to consist of isolated dimerized units of the molecules through some sulfur-sulfur nonbonded contacts: monoclinic, P2(1)/c, a = 9.534(2) Angstrom, b = 18.227(2) Angstrom, c = 17.775(2) Angstrom, beta = 94.39(1)degrees, Z = 4. [References: 56]