Reductive Disproportionation of CO2 Mediated by Bimetallic Nickelate(–I)/Group 13 Complexes

Matthew V. Vollmer; Ryan C. Cammarota; Connie C. Lu

doi:10.1002/ejic.201801452

Reductive Disproportionation of CO₂ Mediated by Bimetallic Nickelate(–I)/Group 13 Complexes

Matthew V. Vollmer
, Ryan C. Cammarota
, Connie C. Lu

Chemistry (Twin Cities)

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

26 Scopus citations

Abstract

The reactivity of bimetallic nickel(–I)/group 13 complexes towards carbon dioxide is presented. Reaction of the anionic [NiML]^– complexes, where M is Al or Ga, and L is {N[(o-C₆H₄)NCH₂PiPr₂]₃}^3–, with CO₂ (1 atm) results in reductive disproportion of CO₂ to afford CO₃^2–, NiML, and the mono-carbonyl adducts, (CO)NiML. The (CO)NiML complexes, where M is Al, Ga, or In, were independently synthesized and characterized. The extent of CO activation varies slightly across the different group 13 ions, where the CO stretching frequency increases for M = Al < Ga < In.

Original language	English (US)
Pages (from-to)	2140-2145
Number of pages	6
Journal	European Journal of Inorganic Chemistry
Volume	2019
Issue number	15
DOIs	https://doi.org/10.1002/ejic.201801452
State	Published - Apr 24 2019

Bibliographical note

Funding Information:
This work was supported by the US National Science Foundation (NSF, CHE-1665010). M. V. V. and R. C. C. were supported by Doctoral Dissertation Fellowships from the University of Minnesota. The authors thank Dr. Victor G. Young, Jr. for assistance with crystallographic studies. X-ray diffraction experiments were performed using a crystal diffractometer purchased through a grant from NSF (MRI-1229400) and the University of Minnesota.

Publisher Copyright:
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

Carbon dioxide
Disproportionation
Group 13 elements
Lewis acids
Metalloradicals
Redox chemistry

Publisher link

10.1002/ejic.201801452

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title = "Reductive Disproportionation of CO2 Mediated by Bimetallic Nickelate({\textendash}I)/Group 13 Complexes",

abstract = "The reactivity of bimetallic nickel({\textendash}I)/group 13 complexes towards carbon dioxide is presented. Reaction of the anionic [NiML]{\textendash} complexes, where M is Al or Ga, and L is \{N[(o-C6H4)NCH2PiPr2]3\}3{\textendash}, with CO2 (1 atm) results in reductive disproportion of CO2 to afford CO32{\textendash}, NiML, and the mono-carbonyl adducts, (CO)NiML. The (CO)NiML complexes, where M is Al, Ga, or In, were independently synthesized and characterized. The extent of CO activation varies slightly across the different group 13 ions, where the CO stretching frequency increases for M = Al < Ga < In.",

keywords = "Carbon dioxide, Disproportionation, Group 13 elements, Lewis acids, Metalloradicals, Redox chemistry",

author = "Vollmer, \{Matthew V.\} and Cammarota, \{Ryan C.\} and Lu, \{Connie C.\}",

note = "Funding Information: This work was supported by the US National Science Foundation (NSF, CHE-1665010). M. V. V. and R. C. C. were supported by Doctoral Dissertation Fellowships from the University of Minnesota. The authors thank Dr. Victor G. Young, Jr. for assistance with crystallographic studies. X-ray diffraction experiments were performed using a crystal diffractometer purchased through a grant from NSF (MRI-1229400) and the University of Minnesota. Publisher Copyright: {\textcopyright} 2019 WILEY-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2019",

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T1 - Reductive Disproportionation of CO2 Mediated by Bimetallic Nickelate(–I)/Group 13 Complexes

AU - Vollmer, Matthew V.

AU - Cammarota, Ryan C.

AU - Lu, Connie C.

N1 - Funding Information: This work was supported by the US National Science Foundation (NSF, CHE-1665010). M. V. V. and R. C. C. were supported by Doctoral Dissertation Fellowships from the University of Minnesota. The authors thank Dr. Victor G. Young, Jr. for assistance with crystallographic studies. X-ray diffraction experiments were performed using a crystal diffractometer purchased through a grant from NSF (MRI-1229400) and the University of Minnesota. Publisher Copyright: © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2019/4/24

Y1 - 2019/4/24

N2 - The reactivity of bimetallic nickel(–I)/group 13 complexes towards carbon dioxide is presented. Reaction of the anionic [NiML]– complexes, where M is Al or Ga, and L is {N[(o-C6H4)NCH2PiPr2]3}3–, with CO2 (1 atm) results in reductive disproportion of CO2 to afford CO32–, NiML, and the mono-carbonyl adducts, (CO)NiML. The (CO)NiML complexes, where M is Al, Ga, or In, were independently synthesized and characterized. The extent of CO activation varies slightly across the different group 13 ions, where the CO stretching frequency increases for M = Al < Ga < In.

AB - The reactivity of bimetallic nickel(–I)/group 13 complexes towards carbon dioxide is presented. Reaction of the anionic [NiML]– complexes, where M is Al or Ga, and L is {N[(o-C6H4)NCH2PiPr2]3}3–, with CO2 (1 atm) results in reductive disproportion of CO2 to afford CO32–, NiML, and the mono-carbonyl adducts, (CO)NiML. The (CO)NiML complexes, where M is Al, Ga, or In, were independently synthesized and characterized. The extent of CO activation varies slightly across the different group 13 ions, where the CO stretching frequency increases for M = Al < Ga < In.

KW - Carbon dioxide

KW - Disproportionation

KW - Group 13 elements

KW - Lewis acids

KW - Metalloradicals

KW - Redox chemistry

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