Synthesis, structure, and electrochemical studies of μ3222-C 60 triosmium complexes

Hyunjoon Song, Kwangyeol Lee, Joon T. Park, Moon-Gun Choi

Research output: Contribution to journalArticle

47 Citations (Scopus)

Abstract

Two μ3222-C 60 complexes, Os3(CO)8(PPh3)(μ3222-C60) (8) and Os3(CO)7(PMe3)23222-C 60) (9), have been prepared by decarbonylation of Os3(CO)93222-C60) (6) with Me3NO/MeCN in the presence of phosphine ligands. The molecular structure of 8 has been determined by a single-crystal X-ray diffraction study. The structure of 8 is derived from that of Os3(CO)11(PPh3) by replacing three axial carbonyl ligands with a μ3-face-capping C6 ring of C60. The 13C NMR spectra (C60 region) of 6 and Os3(CO)8(PMe3)(μ3222-C60) (7) show 11 sp2 and 1 sp3 carbon resonances and 29 sp2 and 3 sp3 carbon resonances, respectively, which are consistent with C3v and Cs symmetric nature of the two complexes in solution. Electrochemical properties of 6, 7, and 9 have been studied by cyclic voltammetry (CV) in 1,2-dichlorobenzene (DCB) solutions. The general features of CV curves have revealed four reversible redox couples for 6 and 7 and three for 9 in the DCB potential window. The μ3222-C 60 complexes, 6, 7, and 9, show a remarkable electrochemical stability compared to the known η2-C60 triosmium carbonyl complexes. The CV results suggest that a C60-mediated electron transfer to the triosmium center takes place in 6 and 7, but three successive C60-localized reductions occur in 9.

Original languageEnglish
Pages (from-to)4477-4483
Number of pages7
JournalOrganometallics
Volume17
Issue number20
Publication statusPublished - 1998 Sep 28

Fingerprint

Cyclic voltammetry
phosphine
ligands
carbon
Carbon
synthesis
phosphines
Ligands
electron transfer
molecular structure
Electrochemical properties
nuclear magnetic resonance
Molecular structure
rings
single crystals
curves
diffraction
Nuclear magnetic resonance
Single crystals
X ray diffraction

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Song, H., Lee, K., Park, J. T., & Choi, M-G. (1998). Synthesis, structure, and electrochemical studies of μ3222-C 60 triosmium complexes. Organometallics, 17(20), 4477-4483.
Song, Hyunjoon ; Lee, Kwangyeol ; Park, Joon T. ; Choi, Moon-Gun. / Synthesis, structure, and electrochemical studies of μ3222-C 60 triosmium complexes. In: Organometallics. 1998 ; Vol. 17, No. 20. pp. 4477-4483.
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title = "Synthesis, structure, and electrochemical studies of μ3-η2,η2,η2-C 60 triosmium complexes",
abstract = "Two μ3-η2,η2,η2-C 60 complexes, Os3(CO)8(PPh3)(μ3-η 2,η2,η2-C60) (8) and Os3(CO)7(PMe3)2(μ 3-η2,η2,η2-C 60) (9), have been prepared by decarbonylation of Os3(CO)9(μ3-η2,η 2,η2-C60) (6) with Me3NO/MeCN in the presence of phosphine ligands. The molecular structure of 8 has been determined by a single-crystal X-ray diffraction study. The structure of 8 is derived from that of Os3(CO)11(PPh3) by replacing three axial carbonyl ligands with a μ3-face-capping C6 ring of C60. The 13C NMR spectra (C60 region) of 6 and Os3(CO)8(PMe3)(μ3-η 2,η2,η2-C60) (7) show 11 sp2 and 1 sp3 carbon resonances and 29 sp2 and 3 sp3 carbon resonances, respectively, which are consistent with C3v and Cs symmetric nature of the two complexes in solution. Electrochemical properties of 6, 7, and 9 have been studied by cyclic voltammetry (CV) in 1,2-dichlorobenzene (DCB) solutions. The general features of CV curves have revealed four reversible redox couples for 6 and 7 and three for 9 in the DCB potential window. The μ3-η2,η2,η2-C 60 complexes, 6, 7, and 9, show a remarkable electrochemical stability compared to the known η2-C60 triosmium carbonyl complexes. The CV results suggest that a C60-mediated electron transfer to the triosmium center takes place in 6 and 7, but three successive C60-localized reductions occur in 9.",
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Song, H, Lee, K, Park, JT & Choi, M-G 1998, 'Synthesis, structure, and electrochemical studies of μ3222-C 60 triosmium complexes', Organometallics, vol. 17, no. 20, pp. 4477-4483.

Synthesis, structure, and electrochemical studies of μ3222-C 60 triosmium complexes. / Song, Hyunjoon; Lee, Kwangyeol; Park, Joon T.; Choi, Moon-Gun.

In: Organometallics, Vol. 17, No. 20, 28.09.1998, p. 4477-4483.

Research output: Contribution to journalArticle

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N2 - Two μ3-η2,η2,η2-C 60 complexes, Os3(CO)8(PPh3)(μ3-η 2,η2,η2-C60) (8) and Os3(CO)7(PMe3)2(μ 3-η2,η2,η2-C 60) (9), have been prepared by decarbonylation of Os3(CO)9(μ3-η2,η 2,η2-C60) (6) with Me3NO/MeCN in the presence of phosphine ligands. The molecular structure of 8 has been determined by a single-crystal X-ray diffraction study. The structure of 8 is derived from that of Os3(CO)11(PPh3) by replacing three axial carbonyl ligands with a μ3-face-capping C6 ring of C60. The 13C NMR spectra (C60 region) of 6 and Os3(CO)8(PMe3)(μ3-η 2,η2,η2-C60) (7) show 11 sp2 and 1 sp3 carbon resonances and 29 sp2 and 3 sp3 carbon resonances, respectively, which are consistent with C3v and Cs symmetric nature of the two complexes in solution. Electrochemical properties of 6, 7, and 9 have been studied by cyclic voltammetry (CV) in 1,2-dichlorobenzene (DCB) solutions. The general features of CV curves have revealed four reversible redox couples for 6 and 7 and three for 9 in the DCB potential window. The μ3-η2,η2,η2-C 60 complexes, 6, 7, and 9, show a remarkable electrochemical stability compared to the known η2-C60 triosmium carbonyl complexes. The CV results suggest that a C60-mediated electron transfer to the triosmium center takes place in 6 and 7, but three successive C60-localized reductions occur in 9.

AB - Two μ3-η2,η2,η2-C 60 complexes, Os3(CO)8(PPh3)(μ3-η 2,η2,η2-C60) (8) and Os3(CO)7(PMe3)2(μ 3-η2,η2,η2-C 60) (9), have been prepared by decarbonylation of Os3(CO)9(μ3-η2,η 2,η2-C60) (6) with Me3NO/MeCN in the presence of phosphine ligands. The molecular structure of 8 has been determined by a single-crystal X-ray diffraction study. The structure of 8 is derived from that of Os3(CO)11(PPh3) by replacing three axial carbonyl ligands with a μ3-face-capping C6 ring of C60. The 13C NMR spectra (C60 region) of 6 and Os3(CO)8(PMe3)(μ3-η 2,η2,η2-C60) (7) show 11 sp2 and 1 sp3 carbon resonances and 29 sp2 and 3 sp3 carbon resonances, respectively, which are consistent with C3v and Cs symmetric nature of the two complexes in solution. Electrochemical properties of 6, 7, and 9 have been studied by cyclic voltammetry (CV) in 1,2-dichlorobenzene (DCB) solutions. The general features of CV curves have revealed four reversible redox couples for 6 and 7 and three for 9 in the DCB potential window. The μ3-η2,η2,η2-C 60 complexes, 6, 7, and 9, show a remarkable electrochemical stability compared to the known η2-C60 triosmium carbonyl complexes. The CV results suggest that a C60-mediated electron transfer to the triosmium center takes place in 6 and 7, but three successive C60-localized reductions occur in 9.

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