Diosmium(III) compounds supported by 2-anilinopyridinate and novel alkynyl derivatives

Yan Hui Shi, Wei Zhong Chen, Kevin D. John, Ryan E. Da Re, Joshua Cohn, Guo Lin Xu, Judith L. Eglin, Alfred P. Sattelberger, Curtis R. Hare, Tong Ren

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Abstract

The reaction between Os2(OAc)4Cl2 and Hap (Hap is 2-anilinopyridine) under prolonged refluxing conditions resulted in an OsIII 2 compound, Os2(ap)4Cl 2 (1), that can be crystallized as either the cis-(2,2) isomer from a CH3OH-CH2-Cl2 solution or the (3,1) isomer from a hexanes-CH2Cl2 solution. Compound 1 undergoes facile reactions with LiC2Y to yield a series of Os 2(ap)4(C2Y)2 compounds with Y as Ph (2), ferrocenyl (3), SiMe3 (4), and C2SiMe3 (5). X-ray diffraction study of compound 2 reveals solvent-dependent isomerism similar to that of the parent compound 1. Compound 1 has Os-Os distances of 2.3937(8) and 2.3913(8) Å for the cis-(2,2) and (3,1) isomers, respectively, and is paramagnetic (S = 1). Both the ethynyl derivatives 2-4 and butadiynyl derivative 5 are diamagnetic and have Os-Os distances of 2.456(1), 2.471(1), and 2.481(1) Å for the cis-(2,2) and (3,1) isomers of 2 and (3,1) isomer of 4, respectively. Compounds 1-5 exhibit multiple one-electron redox couples in their cyclic voltammograms, including a reversible Os 2(8+/7+) couple for 2. Resonance Raman spectra of both compounds 1 and 2 are reported.

Original languageEnglish (US)
Pages (from-to)5719-5727
Number of pages9
JournalInorganic Chemistry
Volume44
Issue number16
DOIs
StatePublished - Aug 8 2005

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Isomers
isomers
Derivatives
Hexanes
Raman scattering
Raman spectra
X ray diffraction
Electrons
diffraction
electrons
x rays

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Shi, Y. H., Chen, W. Z., John, K. D., Da Re, R. E., Cohn, J., Xu, G. L., ... Ren, T. (2005). Diosmium(III) compounds supported by 2-anilinopyridinate and novel alkynyl derivatives. Inorganic Chemistry, 44(16), 5719-5727. https://doi.org/10.1021/ic050496r

Diosmium(III) compounds supported by 2-anilinopyridinate and novel alkynyl derivatives. / Shi, Yan Hui; Chen, Wei Zhong; John, Kevin D.; Da Re, Ryan E.; Cohn, Joshua; Xu, Guo Lin; Eglin, Judith L.; Sattelberger, Alfred P.; Hare, Curtis R.; Ren, Tong.

In: Inorganic Chemistry, Vol. 44, No. 16, 08.08.2005, p. 5719-5727.

Research output: Contribution to journalArticle

Shi, YH, Chen, WZ, John, KD, Da Re, RE, Cohn, J, Xu, GL, Eglin, JL, Sattelberger, AP, Hare, CR & Ren, T 2005, 'Diosmium(III) compounds supported by 2-anilinopyridinate and novel alkynyl derivatives', Inorganic Chemistry, vol. 44, no. 16, pp. 5719-5727. https://doi.org/10.1021/ic050496r
Shi, Yan Hui ; Chen, Wei Zhong ; John, Kevin D. ; Da Re, Ryan E. ; Cohn, Joshua ; Xu, Guo Lin ; Eglin, Judith L. ; Sattelberger, Alfred P. ; Hare, Curtis R. ; Ren, Tong. / Diosmium(III) compounds supported by 2-anilinopyridinate and novel alkynyl derivatives. In: Inorganic Chemistry. 2005 ; Vol. 44, No. 16. pp. 5719-5727.
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abstract = "The reaction between Os2(OAc)4Cl2 and Hap (Hap is 2-anilinopyridine) under prolonged refluxing conditions resulted in an OsIII 2 compound, Os2(ap)4Cl 2 (1), that can be crystallized as either the cis-(2,2) isomer from a CH3OH-CH2-Cl2 solution or the (3,1) isomer from a hexanes-CH2Cl2 solution. Compound 1 undergoes facile reactions with LiC2Y to yield a series of Os 2(ap)4(C2Y)2 compounds with Y as Ph (2), ferrocenyl (3), SiMe3 (4), and C2SiMe3 (5). X-ray diffraction study of compound 2 reveals solvent-dependent isomerism similar to that of the parent compound 1. Compound 1 has Os-Os distances of 2.3937(8) and 2.3913(8) {\AA} for the cis-(2,2) and (3,1) isomers, respectively, and is paramagnetic (S = 1). Both the ethynyl derivatives 2-4 and butadiynyl derivative 5 are diamagnetic and have Os-Os distances of 2.456(1), 2.471(1), and 2.481(1) {\AA} for the cis-(2,2) and (3,1) isomers of 2 and (3,1) isomer of 4, respectively. Compounds 1-5 exhibit multiple one-electron redox couples in their cyclic voltammograms, including a reversible Os 2(8+/7+) couple for 2. Resonance Raman spectra of both compounds 1 and 2 are reported.",
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AU - Da Re, Ryan E.

AU - Cohn, Joshua

AU - Xu, Guo Lin

AU - Eglin, Judith L.

AU - Sattelberger, Alfred P.

AU - Hare, Curtis R.

AU - Ren, Tong

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N2 - The reaction between Os2(OAc)4Cl2 and Hap (Hap is 2-anilinopyridine) under prolonged refluxing conditions resulted in an OsIII 2 compound, Os2(ap)4Cl 2 (1), that can be crystallized as either the cis-(2,2) isomer from a CH3OH-CH2-Cl2 solution or the (3,1) isomer from a hexanes-CH2Cl2 solution. Compound 1 undergoes facile reactions with LiC2Y to yield a series of Os 2(ap)4(C2Y)2 compounds with Y as Ph (2), ferrocenyl (3), SiMe3 (4), and C2SiMe3 (5). X-ray diffraction study of compound 2 reveals solvent-dependent isomerism similar to that of the parent compound 1. Compound 1 has Os-Os distances of 2.3937(8) and 2.3913(8) Å for the cis-(2,2) and (3,1) isomers, respectively, and is paramagnetic (S = 1). Both the ethynyl derivatives 2-4 and butadiynyl derivative 5 are diamagnetic and have Os-Os distances of 2.456(1), 2.471(1), and 2.481(1) Å for the cis-(2,2) and (3,1) isomers of 2 and (3,1) isomer of 4, respectively. Compounds 1-5 exhibit multiple one-electron redox couples in their cyclic voltammograms, including a reversible Os 2(8+/7+) couple for 2. Resonance Raman spectra of both compounds 1 and 2 are reported.

AB - The reaction between Os2(OAc)4Cl2 and Hap (Hap is 2-anilinopyridine) under prolonged refluxing conditions resulted in an OsIII 2 compound, Os2(ap)4Cl 2 (1), that can be crystallized as either the cis-(2,2) isomer from a CH3OH-CH2-Cl2 solution or the (3,1) isomer from a hexanes-CH2Cl2 solution. Compound 1 undergoes facile reactions with LiC2Y to yield a series of Os 2(ap)4(C2Y)2 compounds with Y as Ph (2), ferrocenyl (3), SiMe3 (4), and C2SiMe3 (5). X-ray diffraction study of compound 2 reveals solvent-dependent isomerism similar to that of the parent compound 1. Compound 1 has Os-Os distances of 2.3937(8) and 2.3913(8) Å for the cis-(2,2) and (3,1) isomers, respectively, and is paramagnetic (S = 1). Both the ethynyl derivatives 2-4 and butadiynyl derivative 5 are diamagnetic and have Os-Os distances of 2.456(1), 2.471(1), and 2.481(1) Å for the cis-(2,2) and (3,1) isomers of 2 and (3,1) isomer of 4, respectively. Compounds 1-5 exhibit multiple one-electron redox couples in their cyclic voltammograms, including a reversible Os 2(8+/7+) couple for 2. Resonance Raman spectra of both compounds 1 and 2 are reported.

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