Syntheses, structures, and electrochemical properties of Os 3(CO)9-n(CNCH2Ph)n3- η2: η22-C60) (n = 2-4)

Chang Yeon Lee, Bo Keun Park, Jung Hee Yoon, Chang Seop Hong, Joon T. Park

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Benzyl isocyanide-substituted C60-triosmium complexes, Os 3(CO)9-n(CNCH2Ph)n3- η222-C60) (n = 2 (3), 3 (4), and 4 (5)), have been prepared by reactions of either Os 3(CO)932: η22-C60) (1) or its lesser isocyanide-substituted complexes with appropriate amounts of (triphenylphosphino)benzylimine (PhCH2N=PPh3). Compounds 3-5 have been characterized by spectroscopic (IR, MS, 1H and 13C NMR) methods, cyclic voltammetry, and X-ray diffraction studies. Single-crystal X-ray diffraction studies reveal that isomer 3a has two inequivalent equatorial isocyanide ligands as a cis,trans-1,2-isomer and isomer 4a has three equivalent equatorial isocyanide ligands as a 1,2,3-isomer with C3 symmetry. In compound 5, one benzyl isocyanide is axially coordinated to an osmium atom, whereas the other three benzyl isocyanide ligands are equatorially coordinated to each osmium atom. 1H and 13C NMR data, however, indicate that compound 3 exists as a mixture of 1,2- (3a) and 1,1-isomers (3b) in a ratio of 7:1, compound 4 as a mixture of 1,2,3- (4a) and 1,1,2-isomers (4b) in a ratio of 1:1, and compound 5, interestingly, as a single species of a 1,1,2,3-isomer in solution. The cyclic voltammetric studies reveal that all the CVs of 3-5 and related Os 3(CO)8(CNCH2Ph)(μ3- η222-C60) (2) show four reversible redox waves that correspond to a one-electron process each with the third and fourth waves overlapped within the chlorobenzene solvent potential window. As more isocyanide ligands are coordinated in 2-5, all the corresponding half-wave potentials are gradually shifted to more negative potentials, reflecting the electrondonor property of the isocyanide ligand. Furthermore, C60-mediated electron delocalization from C60 to the triosmium center takes place in the trianionic species of 2-5. The two isomers of 3 and 4 apparently undergo an equivalent electrochemical process, respectively.

Original languageEnglish
Pages (from-to)4634-4642
Number of pages9
JournalOrganometallics
Volume25
Issue number19
DOIs
Publication statusPublished - 2006 Sep 11

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Cyanides
Electrochemical properties
Isomers
isomers
synthesis
Ligands
ligands
Osmium
osmium
Nuclear magnetic resonance
X ray diffraction
Atoms
nuclear magnetic resonance
chlorobenzenes
Electrons
diffraction
Cyclic voltammetry
atoms
electrons
x rays

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Syntheses, structures, and electrochemical properties of Os 3(CO)9-n(CNCH2Ph)n3- η2 : η22-C60) (n = 2-4). / Lee, Chang Yeon; Park, Bo Keun; Yoon, Jung Hee; Hong, Chang Seop; Park, Joon T.

In: Organometallics, Vol. 25, No. 19, 11.09.2006, p. 4634-4642.

Research output: Contribution to journalArticle

Lee, Chang Yeon ; Park, Bo Keun ; Yoon, Jung Hee ; Hong, Chang Seop ; Park, Joon T. / Syntheses, structures, and electrochemical properties of Os 3(CO)9-n(CNCH2Ph)n3- η2 : η22-C60) (n = 2-4). In: Organometallics. 2006 ; Vol. 25, No. 19. pp. 4634-4642.
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title = "Syntheses, structures, and electrochemical properties of Os 3(CO)9-n(CNCH2Ph)n(μ3- η2: η2:η2-C60) (n = 2-4)",
abstract = "Benzyl isocyanide-substituted C60-triosmium complexes, Os 3(CO)9-n(CNCH2Ph)n(μ3- η2:η2:η2-C60) (n = 2 (3), 3 (4), and 4 (5)), have been prepared by reactions of either Os 3(CO)9(μ3-η2: η2:η2-C60) (1) or its lesser isocyanide-substituted complexes with appropriate amounts of (triphenylphosphino)benzylimine (PhCH2N=PPh3). Compounds 3-5 have been characterized by spectroscopic (IR, MS, 1H and 13C NMR) methods, cyclic voltammetry, and X-ray diffraction studies. Single-crystal X-ray diffraction studies reveal that isomer 3a has two inequivalent equatorial isocyanide ligands as a cis,trans-1,2-isomer and isomer 4a has three equivalent equatorial isocyanide ligands as a 1,2,3-isomer with C3 symmetry. In compound 5, one benzyl isocyanide is axially coordinated to an osmium atom, whereas the other three benzyl isocyanide ligands are equatorially coordinated to each osmium atom. 1H and 13C NMR data, however, indicate that compound 3 exists as a mixture of 1,2- (3a) and 1,1-isomers (3b) in a ratio of 7:1, compound 4 as a mixture of 1,2,3- (4a) and 1,1,2-isomers (4b) in a ratio of 1:1, and compound 5, interestingly, as a single species of a 1,1,2,3-isomer in solution. The cyclic voltammetric studies reveal that all the CVs of 3-5 and related Os 3(CO)8(CNCH2Ph)(μ3- η2:η2:η2-C60) (2) show four reversible redox waves that correspond to a one-electron process each with the third and fourth waves overlapped within the chlorobenzene solvent potential window. As more isocyanide ligands are coordinated in 2-5, all the corresponding half-wave potentials are gradually shifted to more negative potentials, reflecting the electrondonor property of the isocyanide ligand. Furthermore, C60-mediated electron delocalization from C60 to the triosmium center takes place in the trianionic species of 2-5. The two isomers of 3 and 4 apparently undergo an equivalent electrochemical process, respectively.",
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T1 - Syntheses, structures, and electrochemical properties of Os 3(CO)9-n(CNCH2Ph)n(μ3- η2

T2 - η2:η2-C60) (n = 2-4)

AU - Lee, Chang Yeon

AU - Park, Bo Keun

AU - Yoon, Jung Hee

AU - Hong, Chang Seop

AU - Park, Joon T.

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N2 - Benzyl isocyanide-substituted C60-triosmium complexes, Os 3(CO)9-n(CNCH2Ph)n(μ3- η2:η2:η2-C60) (n = 2 (3), 3 (4), and 4 (5)), have been prepared by reactions of either Os 3(CO)9(μ3-η2: η2:η2-C60) (1) or its lesser isocyanide-substituted complexes with appropriate amounts of (triphenylphosphino)benzylimine (PhCH2N=PPh3). Compounds 3-5 have been characterized by spectroscopic (IR, MS, 1H and 13C NMR) methods, cyclic voltammetry, and X-ray diffraction studies. Single-crystal X-ray diffraction studies reveal that isomer 3a has two inequivalent equatorial isocyanide ligands as a cis,trans-1,2-isomer and isomer 4a has three equivalent equatorial isocyanide ligands as a 1,2,3-isomer with C3 symmetry. In compound 5, one benzyl isocyanide is axially coordinated to an osmium atom, whereas the other three benzyl isocyanide ligands are equatorially coordinated to each osmium atom. 1H and 13C NMR data, however, indicate that compound 3 exists as a mixture of 1,2- (3a) and 1,1-isomers (3b) in a ratio of 7:1, compound 4 as a mixture of 1,2,3- (4a) and 1,1,2-isomers (4b) in a ratio of 1:1, and compound 5, interestingly, as a single species of a 1,1,2,3-isomer in solution. The cyclic voltammetric studies reveal that all the CVs of 3-5 and related Os 3(CO)8(CNCH2Ph)(μ3- η2:η2:η2-C60) (2) show four reversible redox waves that correspond to a one-electron process each with the third and fourth waves overlapped within the chlorobenzene solvent potential window. As more isocyanide ligands are coordinated in 2-5, all the corresponding half-wave potentials are gradually shifted to more negative potentials, reflecting the electrondonor property of the isocyanide ligand. Furthermore, C60-mediated electron delocalization from C60 to the triosmium center takes place in the trianionic species of 2-5. The two isomers of 3 and 4 apparently undergo an equivalent electrochemical process, respectively.

AB - Benzyl isocyanide-substituted C60-triosmium complexes, Os 3(CO)9-n(CNCH2Ph)n(μ3- η2:η2:η2-C60) (n = 2 (3), 3 (4), and 4 (5)), have been prepared by reactions of either Os 3(CO)9(μ3-η2: η2:η2-C60) (1) or its lesser isocyanide-substituted complexes with appropriate amounts of (triphenylphosphino)benzylimine (PhCH2N=PPh3). Compounds 3-5 have been characterized by spectroscopic (IR, MS, 1H and 13C NMR) methods, cyclic voltammetry, and X-ray diffraction studies. Single-crystal X-ray diffraction studies reveal that isomer 3a has two inequivalent equatorial isocyanide ligands as a cis,trans-1,2-isomer and isomer 4a has three equivalent equatorial isocyanide ligands as a 1,2,3-isomer with C3 symmetry. In compound 5, one benzyl isocyanide is axially coordinated to an osmium atom, whereas the other three benzyl isocyanide ligands are equatorially coordinated to each osmium atom. 1H and 13C NMR data, however, indicate that compound 3 exists as a mixture of 1,2- (3a) and 1,1-isomers (3b) in a ratio of 7:1, compound 4 as a mixture of 1,2,3- (4a) and 1,1,2-isomers (4b) in a ratio of 1:1, and compound 5, interestingly, as a single species of a 1,1,2,3-isomer in solution. The cyclic voltammetric studies reveal that all the CVs of 3-5 and related Os 3(CO)8(CNCH2Ph)(μ3- η2:η2:η2-C60) (2) show four reversible redox waves that correspond to a one-electron process each with the third and fourth waves overlapped within the chlorobenzene solvent potential window. As more isocyanide ligands are coordinated in 2-5, all the corresponding half-wave potentials are gradually shifted to more negative potentials, reflecting the electrondonor property of the isocyanide ligand. Furthermore, C60-mediated electron delocalization from C60 to the triosmium center takes place in the trianionic species of 2-5. The two isomers of 3 and 4 apparently undergo an equivalent electrochemical process, respectively.

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