Efficient Reduction of Carbon Dioxide to Methanol Equivalents Catalyzed by Two-Coordinate Amido-Germanium(II) and -Tin(II) Hydride Complexes

Terrance J. Hadlington, Christos E Kefalidis, Laurent Maron, Cameron Jones

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The bulky amido-germanium(II) and -tin(II) hydride complexes, LEH [E = Ge or Sn; L = -N(Ar) (SiPri3); Ar = C6H2Pri{C(H)Ph2}2-4,2,6], which are two-coordinate in solution, are shown to be efficient and highly selective "single-site" catalysts for the reduction of CO2 to methanol equivalents (MeOBR2), using HBpin or HBcat as the hydrogen source. LSnH is the most active non-transition metal catalyst yet reported for such reductions, yielding turnover frequencies of up to 1188 h-1 at room temperature. Computational studies have identified two thermodynamically and kinetically viable catalytic pathways by which these reductions may operate. Spectroscopic investigations have identified several reaction intermediates, which leads to the conclusion that one of these reaction pathways predominates in the experimental situation. Stoichiometric reactivity studies have shed further light on the reaction mechanisms in operation and indicate that the involvement of the second reaction pathway cannot be ruled out. This study highlights the potential of relatively cheap, main group complexes as viable alternatives to transition metal-based systems in the catalytic transformation of small molecules. (Chemical Equation Presented).

Original languageEnglish
Pages (from-to)1853-1859
Number of pages7
JournalACS Catalysis
Volume7
Issue number3
DOIs
Publication statusPublished - 3 Mar 2017

Keywords

  • catalysis
  • CO
  • germanium
  • low-coordinate
  • reduction
  • tin

Cite this

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title = "Efficient Reduction of Carbon Dioxide to Methanol Equivalents Catalyzed by Two-Coordinate Amido-Germanium(II) and -Tin(II) Hydride Complexes",
abstract = "The bulky amido-germanium(II) and -tin(II) hydride complexes, L†EH [E = Ge or Sn; L† = -N(Ar†) (SiPri3); Ar† = C6H2Pri{C(H)Ph2}2-4,2,6], which are two-coordinate in solution, are shown to be efficient and highly selective {"}single-site{"} catalysts for the reduction of CO2 to methanol equivalents (MeOBR2), using HBpin or HBcat as the hydrogen source. L†SnH is the most active non-transition metal catalyst yet reported for such reductions, yielding turnover frequencies of up to 1188 h-1 at room temperature. Computational studies have identified two thermodynamically and kinetically viable catalytic pathways by which these reductions may operate. Spectroscopic investigations have identified several reaction intermediates, which leads to the conclusion that one of these reaction pathways predominates in the experimental situation. Stoichiometric reactivity studies have shed further light on the reaction mechanisms in operation and indicate that the involvement of the second reaction pathway cannot be ruled out. This study highlights the potential of relatively cheap, main group complexes as viable alternatives to transition metal-based systems in the catalytic transformation of small molecules. (Chemical Equation Presented).",
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author = "Hadlington, {Terrance J.} and Kefalidis, {Christos E} and Laurent Maron and Cameron Jones",
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Efficient Reduction of Carbon Dioxide to Methanol Equivalents Catalyzed by Two-Coordinate Amido-Germanium(II) and -Tin(II) Hydride Complexes. / Hadlington, Terrance J.; Kefalidis, Christos E; Maron, Laurent; Jones, Cameron.

In: ACS Catalysis, Vol. 7, No. 3, 03.03.2017, p. 1853-1859.

Research output: Contribution to journalArticleResearchpeer-review

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T1 - Efficient Reduction of Carbon Dioxide to Methanol Equivalents Catalyzed by Two-Coordinate Amido-Germanium(II) and -Tin(II) Hydride Complexes

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AU - Maron, Laurent

AU - Jones, Cameron

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AB - The bulky amido-germanium(II) and -tin(II) hydride complexes, L†EH [E = Ge or Sn; L† = -N(Ar†) (SiPri3); Ar† = C6H2Pri{C(H)Ph2}2-4,2,6], which are two-coordinate in solution, are shown to be efficient and highly selective "single-site" catalysts for the reduction of CO2 to methanol equivalents (MeOBR2), using HBpin or HBcat as the hydrogen source. L†SnH is the most active non-transition metal catalyst yet reported for such reductions, yielding turnover frequencies of up to 1188 h-1 at room temperature. Computational studies have identified two thermodynamically and kinetically viable catalytic pathways by which these reductions may operate. Spectroscopic investigations have identified several reaction intermediates, which leads to the conclusion that one of these reaction pathways predominates in the experimental situation. Stoichiometric reactivity studies have shed further light on the reaction mechanisms in operation and indicate that the involvement of the second reaction pathway cannot be ruled out. This study highlights the potential of relatively cheap, main group complexes as viable alternatives to transition metal-based systems in the catalytic transformation of small molecules. (Chemical Equation Presented).

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