Sulfur-rich CpCo(dithiolene) complexes: Isostructural or non-isostructural couples of CpCo(III) with CpNi(III) dithiolene complexes

College

College of Science

Department/Unit

Chemistry

Document Type

Article

Source Title

Journal of Organometallic Chemistry

Volume

695

Issue

21

First Page

2366

Last Page

2375

Publication Date

10-1-2010

Abstract

Eight new sulfur-rich [CpCo(dithiolene)] complexes were synthesized from [Zn(dmit)2]2- as a starting material. The structures, electrochemical behavior and electronic absorption spectra of the sulfur-rich [CpCo(S2C2S2Y)] complexes could be compared with the early data of analogous Ni complexes. [CpCo(pddt)] (Y = -(CH 2)3-), [CpCo(dpdt)] (Y = -CH2C(CH 2)CH2-), [CpCo(bddt)] (Y = -(CH2) 4-), [CpCo(dtdt)] (Y = -CH2SCH2-) and [CpCo(poddt)] (Y = -CH2C(O)CH2-) crystallized in all isostructural with the corresponding paramagnetic [CpNi(dithiolene)] complexes, but [CpCo(dmid)] (Y = CO), [CpCo(dddt)] (Y = -(CH2)2-) and [CpCo(F2pddt)] (Y = -CH2CF2CH2-) crystallized in non-isostructural with them. These molecules are associated with intermolecular short S⋯S contacts in the crystals. [CpCo(F 2pddt)] did not show any remarkable S⋯S contacts but indicated interesting fluorine segregation and Cp⋯Cp face-to-face interactions. Redox potentials of [CpCo(dithiolene)] complexes were obtained with the cyclic voltammetry measurements and dimerized by electrochemical oxidations. Electronic absorption spectra of [CpCo(dithiolene)] complexes showed visible absorption in the range of 585-701 nm as lowest energy wavelengths (ε = 9800-11,800 M-1 cm-1) in solutions, and they were higher energy than those of [CpNi(dithiolene)] complexes (near-IR). © 2010 Elsevier B.V.

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Digitial Object Identifier (DOI)

10.1016/j.jorganchem.2010.05.024

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