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Dithiolate complexes of manganese and rhenium: X-ray structure and properties of an unusual mixed valence cluster Mn-3(CO)(6)(mu-eta(2)-SCH2CH2CH2S)(3)

Begum, N ; Hyder, I ; Kabir, S E ; Hossain, G M G ; Nordlander, Ebbe LU ; Rokhsana, D and Rosenberg, E (2005) In Inorganic Chemistry 44(26). p.9887-9894
Abstract
Treatment of Mn-2(CO)(10) with 3,4-toluenedithiol and 1,2-ethanedithiol in the presence of Me(3)NO(.)2H(2)O in CH2CI2 at room temperature afforded the dinuclear complexes Mn-2(CO)(6)(mu-eta(4)-SC6H3(CH3)S-SC6H3(CH3)S) (1), and Mn-2(CO)(6)(mu-eta(4)-SCH2CH2S-SCH2CH2S) (2), respectively. Similar reactions of Re-2(CO)(10) with 3,4-toluenedithiol, 1,2benzenedithiol, and 1,2-ethanedithiol yielded the dirhenium complexes Re-2(CO)(6)(mu-eta(4)-SC6H3(CH3)S-SC6H3(CH3)S) (3), Re-2(CO)(6)(mu-eta(4)-SCH2SC6H4S) (4), and Re-2(CO)(6)(SCH2CH2S-SCH2CH2S) (5), respectively. In contrast, treatment of Mn2(CO)10 with 1,3-propanedithiol afforded the trimanganese compound Mn-3(CO)(6)(mu-eta(2)-SCH2CH2CH2S)(3) (6), whereas Re2(CO)10 gave only intractable... (More)
Treatment of Mn-2(CO)(10) with 3,4-toluenedithiol and 1,2-ethanedithiol in the presence of Me(3)NO(.)2H(2)O in CH2CI2 at room temperature afforded the dinuclear complexes Mn-2(CO)(6)(mu-eta(4)-SC6H3(CH3)S-SC6H3(CH3)S) (1), and Mn-2(CO)(6)(mu-eta(4)-SCH2CH2S-SCH2CH2S) (2), respectively. Similar reactions of Re-2(CO)(10) with 3,4-toluenedithiol, 1,2benzenedithiol, and 1,2-ethanedithiol yielded the dirhenium complexes Re-2(CO)(6)(mu-eta(4)-SC6H3(CH3)S-SC6H3(CH3)S) (3), Re-2(CO)(6)(mu-eta(4)-SCH2SC6H4S) (4), and Re-2(CO)(6)(SCH2CH2S-SCH2CH2S) (5), respectively. In contrast, treatment of Mn2(CO)10 with 1,3-propanedithiol afforded the trimanganese compound Mn-3(CO)(6)(mu-eta(2)-SCH2CH2CH2S)(3) (6), whereas Re2(CO)10 gave only intractable materials. The molecular structures of 1, 3, and 6 have been determined by single-crystal X-ray diffraction studies. The dimanganese and dirhenium carbonyl compounds 1-5 contain a binucleating disulfide ligand, formed by interligand disulfide bond formation between two dithiolate ligands identical in structure to that of the previously reported dimanganese complex Mn-2(CO)(6)(mu-eta(4)-SC6H4S-SC6H4S). Complex 6, on the other hand, forms a unique example of a mixed-valence trimangenese carbonyl compound containing three bridging 1,3-propanedithiolate ligands. The solution properties of 6 have been investigated by UV-vis and EPR spectroscopies as well as electrochemical techniques. (Less)
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Inorganic Chemistry
volume
44
issue
26
pages
9887 - 9894
publisher
The American Chemical Society (ACS)
external identifiers
  • wos:000234192300043
  • pmid:16363859
  • scopus:31144451606
ISSN
1520-510X
DOI
10.1021/ic050987b
language
English
LU publication?
yes
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The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
id
29c26166-567d-4014-8783-4becb131483c (old id 210536)
date added to LUP
2016-04-01 12:07:05
date last changed
2022-03-13 05:33:52
@article{29c26166-567d-4014-8783-4becb131483c,
  abstract     = {{Treatment of Mn-2(CO)(10) with 3,4-toluenedithiol and 1,2-ethanedithiol in the presence of Me(3)NO(.)2H(2)O in CH2CI2 at room temperature afforded the dinuclear complexes Mn-2(CO)(6)(mu-eta(4)-SC6H3(CH3)S-SC6H3(CH3)S) (1), and Mn-2(CO)(6)(mu-eta(4)-SCH2CH2S-SCH2CH2S) (2), respectively. Similar reactions of Re-2(CO)(10) with 3,4-toluenedithiol, 1,2benzenedithiol, and 1,2-ethanedithiol yielded the dirhenium complexes Re-2(CO)(6)(mu-eta(4)-SC6H3(CH3)S-SC6H3(CH3)S) (3), Re-2(CO)(6)(mu-eta(4)-SCH2SC6H4S) (4), and Re-2(CO)(6)(SCH2CH2S-SCH2CH2S) (5), respectively. In contrast, treatment of Mn2(CO)10 with 1,3-propanedithiol afforded the trimanganese compound Mn-3(CO)(6)(mu-eta(2)-SCH2CH2CH2S)(3) (6), whereas Re2(CO)10 gave only intractable materials. The molecular structures of 1, 3, and 6 have been determined by single-crystal X-ray diffraction studies. The dimanganese and dirhenium carbonyl compounds 1-5 contain a binucleating disulfide ligand, formed by interligand disulfide bond formation between two dithiolate ligands identical in structure to that of the previously reported dimanganese complex Mn-2(CO)(6)(mu-eta(4)-SC6H4S-SC6H4S). Complex 6, on the other hand, forms a unique example of a mixed-valence trimangenese carbonyl compound containing three bridging 1,3-propanedithiolate ligands. The solution properties of 6 have been investigated by UV-vis and EPR spectroscopies as well as electrochemical techniques.}},
  author       = {{Begum, N and Hyder, I and Kabir, S E and Hossain, G M G and Nordlander, Ebbe and Rokhsana, D and Rosenberg, E}},
  issn         = {{1520-510X}},
  language     = {{eng}},
  number       = {{26}},
  pages        = {{9887--9894}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{Inorganic Chemistry}},
  title        = {{Dithiolate complexes of manganese and rhenium: X-ray structure and properties of an unusual mixed valence cluster Mn-3(CO)(6)(mu-eta(2)-SCH2CH2CH2S)(3)}},
  url          = {{http://dx.doi.org/10.1021/ic050987b}},
  doi          = {{10.1021/ic050987b}},
  volume       = {{44}},
  year         = {{2005}},
}