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Pentacoordinate cobalt(III) thiolate and nitrosyl tropocoronand compounds.

Publication ,  Journal Article
Franz, KJ; Doerrer, LH; Spingler, B; Lippard, SJ
Published in: Inorganic chemistry
July 2001

Reaction of [Co(TC-n,m)]+ with (Me4N)(SC6F5), where (TC-n,m) is a tropocoronand with n and m linker chain methylene groups, yielded the thiolate complexes [Co(SC6F5)(TC-3,3)] (1a), and [Co(SC6F5)(TC-4,4)] (2a), which were structurally characterized. Use of more electron-releasing thiolates afforded the [Co(TC-n,m)] reduction product and the corresponding disulfide. The bent nitrosyl complexes [Co(NO)(TC-3,3)] (1b) and [Co(NO)(TC-4,4)] (2b) were synthesized from [Co(TC-n,m)] and NO and their structures were also determined. Compounds 1a and 1b have square-pyramidal geometry like all other structurally characterized [MX(TC-3,3)] complexes. Compounds 2a and 2b have trigonal-bipyramidal stereochemistry, formerly rare for Co(III). Although 1a, 1b, and 2a are paramagnetic, 2b is diamagnetic due to the strong antibonding pi-interaction between the metal and NO pi* orbitals. In the presence of excess NO, [Co(TC-4,4)] exhibited novel reactivity in which a putative Co(N2) adduct formed.

Duke Scholars

Published In

Inorganic chemistry

DOI

EISSN

1520-510X

ISSN

0020-1669

Publication Date

July 2001

Volume

40

Issue

15

Start / End Page

3774 / 3780

Related Subject Headings

  • Inorganic & Nuclear Chemistry
  • 3403 Macromolecular and materials chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0306 Physical Chemistry (incl. Structural)
  • 0302 Inorganic Chemistry
 

Citation

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Franz, K. J., Doerrer, L. H., Spingler, B., & Lippard, S. J. (2001). Pentacoordinate cobalt(III) thiolate and nitrosyl tropocoronand compounds. Inorganic Chemistry, 40(15), 3774–3780. https://doi.org/10.1021/ic010181l
Franz, K. J., L. H. Doerrer, B. Spingler, and S. J. Lippard. “Pentacoordinate cobalt(III) thiolate and nitrosyl tropocoronand compounds.Inorganic Chemistry 40, no. 15 (July 2001): 3774–80. https://doi.org/10.1021/ic010181l.
Franz KJ, Doerrer LH, Spingler B, Lippard SJ. Pentacoordinate cobalt(III) thiolate and nitrosyl tropocoronand compounds. Inorganic chemistry. 2001 Jul;40(15):3774–80.
Franz, K. J., et al. “Pentacoordinate cobalt(III) thiolate and nitrosyl tropocoronand compounds.Inorganic Chemistry, vol. 40, no. 15, July 2001, pp. 3774–80. Epmc, doi:10.1021/ic010181l.
Franz KJ, Doerrer LH, Spingler B, Lippard SJ. Pentacoordinate cobalt(III) thiolate and nitrosyl tropocoronand compounds. Inorganic chemistry. 2001 Jul;40(15):3774–3780.
Journal cover image

Published In

Inorganic chemistry

DOI

EISSN

1520-510X

ISSN

0020-1669

Publication Date

July 2001

Volume

40

Issue

15

Start / End Page

3774 / 3780

Related Subject Headings

  • Inorganic & Nuclear Chemistry
  • 3403 Macromolecular and materials chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0306 Physical Chemistry (incl. Structural)
  • 0302 Inorganic Chemistry