Bimetallic Cobalt-Dinitrogen Complexes: Impact of the Supporting Metal on N2 Activation

Laura J. Clouston, Varinia Bernales, Rebecca K. Carlson, Laura Gagliardi, Connie C. Lu

Research output: Contribution to journalArticle

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Abstract

Expanding a family of cobalt bimetallic complexes, we report the synthesis of the Ti(III) metalloligand, Ti[N(o-(NCH2P(iPr)2)C6H4)3] (abbreviated as TiL), and three heterobimetallics that pair cobalt with an early transition metal ion: CoTiL (1), K(crypt-222)[(N2)CoVL] (2), and K(crypt-222)[(N2)CoCrL] (3). The latter two complexes, along with previously reported K(crypt-222)[(N2)CoAlL] and K(crypt-222)[(N2)Co2L], constitute an isostructural series of cobalt bimetallics that bind dinitrogen in an end-on fashion, i.e. [(N2)CoML]-. The characterization of 1-3 includes cyclic voltammetry, X-ray crystallography, and infrared spectroscopy. The [CoTiL]0/- reduction potential is extremely negative at -3.20 V versus Fc+/Fc. In the CoML series where M is a transition metal, the reduction potentials shift anodically as M is varied across the first-row period. Among the [(N2)CoML]- compounds, the dinitrogen ligand is weakly activated, as evidenced by N-N bond lengths between 1.110(8) and 1.135(4) Å and by N-N stretching frequencies between 1971 and 1995 cm-1. Though changes in νN2 are subtle, the extent of N2 activation decreases across the first-row period. A correlation is found between the [CoML]0/- reduction potentials and N2 activation, where the more cathodic potentials correspond to lower N-N frequencies. Theoretical calculations of the [(N2)CoML]- complexes reveal important variations in the electronic structure and Co-M interactions, which depend on the exact nature of the supporting metal ion, M.

Original languageEnglish (US)
Pages (from-to)9263-9270
Number of pages8
JournalInorganic Chemistry
Volume54
Issue number19
DOIs
StatePublished - Jul 1 2015

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Cobalt
cobalt
Metals
Chemical activation
activation
Transition metals
Metal ions
metals
metal ions
X ray crystallography
transition metals
Bond length
Cyclic voltammetry
Stretching
Electronic structure
Infrared spectroscopy
Ligands
crystallography
infrared spectroscopy
electronic structure

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Bimetallic Cobalt-Dinitrogen Complexes : Impact of the Supporting Metal on N2 Activation. / Clouston, Laura J.; Bernales, Varinia; Carlson, Rebecca K.; Gagliardi, Laura; Lu, Connie C.

In: Inorganic Chemistry, Vol. 54, No. 19, 01.07.2015, p. 9263-9270.

Research output: Contribution to journalArticle

Clouston, Laura J. ; Bernales, Varinia ; Carlson, Rebecca K. ; Gagliardi, Laura ; Lu, Connie C. / Bimetallic Cobalt-Dinitrogen Complexes : Impact of the Supporting Metal on N2 Activation. In: Inorganic Chemistry. 2015 ; Vol. 54, No. 19. pp. 9263-9270.
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AU - Lu, Connie C.

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N2 - Expanding a family of cobalt bimetallic complexes, we report the synthesis of the Ti(III) metalloligand, Ti[N(o-(NCH2P(iPr)2)C6H4)3] (abbreviated as TiL), and three heterobimetallics that pair cobalt with an early transition metal ion: CoTiL (1), K(crypt-222)[(N2)CoVL] (2), and K(crypt-222)[(N2)CoCrL] (3). The latter two complexes, along with previously reported K(crypt-222)[(N2)CoAlL] and K(crypt-222)[(N2)Co2L], constitute an isostructural series of cobalt bimetallics that bind dinitrogen in an end-on fashion, i.e. [(N2)CoML]-. The characterization of 1-3 includes cyclic voltammetry, X-ray crystallography, and infrared spectroscopy. The [CoTiL]0/- reduction potential is extremely negative at -3.20 V versus Fc+/Fc. In the CoML series where M is a transition metal, the reduction potentials shift anodically as M is varied across the first-row period. Among the [(N2)CoML]- compounds, the dinitrogen ligand is weakly activated, as evidenced by N-N bond lengths between 1.110(8) and 1.135(4) Å and by N-N stretching frequencies between 1971 and 1995 cm-1. Though changes in νN2 are subtle, the extent of N2 activation decreases across the first-row period. A correlation is found between the [CoML]0/- reduction potentials and N2 activation, where the more cathodic potentials correspond to lower N-N frequencies. Theoretical calculations of the [(N2)CoML]- complexes reveal important variations in the electronic structure and Co-M interactions, which depend on the exact nature of the supporting metal ion, M.

AB - Expanding a family of cobalt bimetallic complexes, we report the synthesis of the Ti(III) metalloligand, Ti[N(o-(NCH2P(iPr)2)C6H4)3] (abbreviated as TiL), and three heterobimetallics that pair cobalt with an early transition metal ion: CoTiL (1), K(crypt-222)[(N2)CoVL] (2), and K(crypt-222)[(N2)CoCrL] (3). The latter two complexes, along with previously reported K(crypt-222)[(N2)CoAlL] and K(crypt-222)[(N2)Co2L], constitute an isostructural series of cobalt bimetallics that bind dinitrogen in an end-on fashion, i.e. [(N2)CoML]-. The characterization of 1-3 includes cyclic voltammetry, X-ray crystallography, and infrared spectroscopy. The [CoTiL]0/- reduction potential is extremely negative at -3.20 V versus Fc+/Fc. In the CoML series where M is a transition metal, the reduction potentials shift anodically as M is varied across the first-row period. Among the [(N2)CoML]- compounds, the dinitrogen ligand is weakly activated, as evidenced by N-N bond lengths between 1.110(8) and 1.135(4) Å and by N-N stretching frequencies between 1971 and 1995 cm-1. Though changes in νN2 are subtle, the extent of N2 activation decreases across the first-row period. A correlation is found between the [CoML]0/- reduction potentials and N2 activation, where the more cathodic potentials correspond to lower N-N frequencies. Theoretical calculations of the [(N2)CoML]- complexes reveal important variations in the electronic structure and Co-M interactions, which depend on the exact nature of the supporting metal ion, M.

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