Reactivity of a series of isostructural cobalt pincer complexes with CO2, CO, and H+

David W. Shaffer; Samantha I. Johnson; Arnold L. Rheingold; Joseph W. Ziller; William A. Goddard; Robert J. Nielsen; Jenny Y. Yang

doi:10.1021/ic5021725

Reactivity of a series of isostructural cobalt pincer complexes with CO₂, CO, and H⁺

David W. Shaffer
, Samantha I. Johnson
, Arnold L. Rheingold
, Joseph W. Ziller
, William A. Goddard
, Robert J. Nielsen
, Jenny Y. Yang

Research output: Contribution to journal › Article › peer-review

Abstract

The preparation and characterization of a series of isostructural cobalt complexes [Co(t-Bu)₂P^EPy^EP(t-Bu)₂(CH₃CN)₂][BF₄]₂ (Py = pyridine, E = CH₂, NH, O, and X = BF₄ (1a-c)) and the corresponding one-electron reduced analogues [Co(t-Bu)₂P^EPy^EP(t-Bu)₂(CH₃CN)₂][BF₄]₂ (2a-c) are reported. The reactivity of the reduced cobalt complexes with CO₂, CO, and H⁺ to generate intermediates in a CO₂ to CO and H₂O reduction cycle are described. The reduction of 1a-c and subsequent reactivity with CO₂ was investigated by cyclic voltammetry, and for 1a also by infrared spectroelectrochemistry. The corresponding CO complexes of (2a-c) were prepared, and the Co-CO bond strengths were characterized by IR spectroscopy. Quantum mechanical methods (B3LYP-d3 with solvation) were used to characterize the competitive reactivity of the reduced cobalt centers with H⁺ versus CO₂. By investigating a series of isostructural complexes, correlations in reactivity with ligand electron withdrawing effects are made.

Original language	English
Pages (from-to)	13031-13041
Number of pages	11
Journal	Inorganic Chemistry
Volume	53
Issue number	24
DOIs	https://doi.org/10.1021/ic5021725
Publication status	Published - 15 Dec 2014
Externally published	Yes

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@article{137d1f3113df453c9b1c58004cae49f9,

title = "Reactivity of a series of isostructural cobalt pincer complexes with CO2, CO, and H+",

abstract = "The preparation and characterization of a series of isostructural cobalt complexes [Co(t-Bu)2PEPyEP(t-Bu)2(CH3CN)2][BF4]2 (Py = pyridine, E = CH2, NH, O, and X = BF4 (1a-c)) and the corresponding one-electron reduced analogues [Co(t-Bu)2PEPyEP(t-Bu)2(CH3CN)2][BF4]2 (2a-c) are reported. The reactivity of the reduced cobalt complexes with CO2, CO, and H+ to generate intermediates in a CO2 to CO and H2O reduction cycle are described. The reduction of 1a-c and subsequent reactivity with CO2 was investigated by cyclic voltammetry, and for 1a also by infrared spectroelectrochemistry. The corresponding CO complexes of (2a-c) were prepared, and the Co-CO bond strengths were characterized by IR spectroscopy. Quantum mechanical methods (B3LYP-d3 with solvation) were used to characterize the competitive reactivity of the reduced cobalt centers with H+ versus CO2. By investigating a series of isostructural complexes, correlations in reactivity with ligand electron withdrawing effects are made.",

author = "Shaffer, \{David W.\} and Johnson, \{Samantha I.\} and Rheingold, \{Arnold L.\} and Ziller, \{Joseph W.\} and Goddard, \{William A.\} and Nielsen, \{Robert J.\} and Yang, \{Jenny Y.\}",

note = "Publisher Copyright: {\textcopyright} 2014 American Chemical Society.",

year = "2014",

month = dec,

day = "15",

doi = "10.1021/ic5021725",

language = "English",

volume = "53",

pages = "13031--13041",

journal = "Inorganic Chemistry",

issn = "0020-1669",

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T1 - Reactivity of a series of isostructural cobalt pincer complexes with CO2, CO, and H+

AU - Shaffer, David W.

AU - Johnson, Samantha I.

AU - Rheingold, Arnold L.

AU - Ziller, Joseph W.

AU - Goddard, William A.

AU - Nielsen, Robert J.

AU - Yang, Jenny Y.

PY - 2014/12/15

Y1 - 2014/12/15

N2 - The preparation and characterization of a series of isostructural cobalt complexes [Co(t-Bu)2PEPyEP(t-Bu)2(CH3CN)2][BF4]2 (Py = pyridine, E = CH2, NH, O, and X = BF4 (1a-c)) and the corresponding one-electron reduced analogues [Co(t-Bu)2PEPyEP(t-Bu)2(CH3CN)2][BF4]2 (2a-c) are reported. The reactivity of the reduced cobalt complexes with CO2, CO, and H+ to generate intermediates in a CO2 to CO and H2O reduction cycle are described. The reduction of 1a-c and subsequent reactivity with CO2 was investigated by cyclic voltammetry, and for 1a also by infrared spectroelectrochemistry. The corresponding CO complexes of (2a-c) were prepared, and the Co-CO bond strengths were characterized by IR spectroscopy. Quantum mechanical methods (B3LYP-d3 with solvation) were used to characterize the competitive reactivity of the reduced cobalt centers with H+ versus CO2. By investigating a series of isostructural complexes, correlations in reactivity with ligand electron withdrawing effects are made.

AB - The preparation and characterization of a series of isostructural cobalt complexes [Co(t-Bu)2PEPyEP(t-Bu)2(CH3CN)2][BF4]2 (Py = pyridine, E = CH2, NH, O, and X = BF4 (1a-c)) and the corresponding one-electron reduced analogues [Co(t-Bu)2PEPyEP(t-Bu)2(CH3CN)2][BF4]2 (2a-c) are reported. The reactivity of the reduced cobalt complexes with CO2, CO, and H+ to generate intermediates in a CO2 to CO and H2O reduction cycle are described. The reduction of 1a-c and subsequent reactivity with CO2 was investigated by cyclic voltammetry, and for 1a also by infrared spectroelectrochemistry. The corresponding CO complexes of (2a-c) were prepared, and the Co-CO bond strengths were characterized by IR spectroscopy. Quantum mechanical methods (B3LYP-d3 with solvation) were used to characterize the competitive reactivity of the reduced cobalt centers with H+ versus CO2. By investigating a series of isostructural complexes, correlations in reactivity with ligand electron withdrawing effects are made.

UR - https://www.scopus.com/pages/publications/84920202844

U2 - 10.1021/ic5021725

DO - 10.1021/ic5021725

M3 - Article

AN - SCOPUS:84920202844

SN - 0020-1669

VL - 53

SP - 13031

EP - 13041

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 24

ER -

Reactivity of a series of isostructural cobalt pincer complexes with CO₂, CO, and H⁺

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