Synthesis and Characterization of Mononuclear, Pseudotetrahedral Cobalt(III) Compounds

Author(s)
Kozhukh, Julia; Minier, Mikael Antoine; Lippard, Stephen J.
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Abstract
The preparation and characterization of two mononuclear cobalt(III) tropocoronand complexes, [Co(TC-5,5)](BF[subscript 4]) and [Co(TC-6,6)](BPh[subscript 4]), are reported. The cobalt(III) centers exist in rare pseudotetrahedral conformations, with twist angles of 65° and 74° for the [Co(TC-5,5]+ and [Co(TC-6,6)]+ species, respectively. Structural and electrochemical characteristics are compared with those of newly synthesized [Ga(TC-5,5)](GaCl[subscript 4]) and [Ga(TC-6,6)](GaCl[subscript 4]) analogues. The spin state of the pseudotetrahedral [Co(TC-6,6)](BPh[subscript 4]) compound was determined to be S = 2, a change in spin state from the value of S = 1 that occurs in the square-planar and distorted square-planar complexes, [Co(TC-3,3)](X) (X = BPh[subscript 4], BAr′[subscript 4]) and [Co(TC-4,4)](BPh[subscript 4]), respectively.
Date issued
2014-12
URI
http://hdl.handle.net/1721.1/103894
Department
Massachusetts Institute of Technology. Department of Chemistry
Journal
Inorganic Chemistry
Publisher
American Chemical Society (ACS)
Citation
Kozhukh, Julia, Mikael A. Minier, and Stephen J. Lippard. “Synthesis and Characterization of Mononuclear, Pseudotetrahedral Cobalt(III) Compounds.” Inorg. Chem. 54, no. 2 (January 20, 2015): 418–424. © 2014 American Chemical Society.
Version: Final published version
ISSN
0020-1669
1520-510X
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