Title: Evaluating the impacts of amino acids in the second and outer coordination spheres of Rh-bis(diphosphine) complexes for CO2 hydrogenation

Journal Article · · Faraday Discussions
DOI: https://doi.org/10.1039/c8fd00164b · OSTI ID:1571505
ORCiD logo [1];  [1];  [2];  [3];  [4];  [5]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [3]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate; Ferro Corporation, Penn Yan, NY (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate; Rutgers Univ., Piscataway, NJ (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate; Curium, Maryland Heights, MO (United States)
  5. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate; Univ. of Wisconsin-Oshkosh, Oshkosh, WI (United States)
+ Show Author Affiliations

To explore the influence of a biologically inspired second and outer coordination sphere on Rh-bis(diphosphine) CO2 hydrogenation catalysts, a series of five complexes were prepared by varying the substituents on the pendant amine in the P(Et)2CH2NRCH2P(Et)2 ligands (PEtNRPEt), where R consists of methyl ester modified amino acids, including three neutral (glycine methyl ester (GlyOMe), leucine methyl ester (LeuOMe), and phenylalanine methyl ester (PheOMe)), one acidic (aspartic acid dimethyl ester (AspOMe)) and one basic (histidine methyl ester (MeHisOMe)) amino acid esters. The turnover frequencies (TOFs) for CO2 hydrogenation for each of these complexes were compared to those of the non-amino acid containing [Rh(depp)2]+ (depp) and [Rh(PEtNMePEt)2]+ (NMe) complexes. Each complex is catalytically active for CO2 hydrogenation to formate under mild conditions in THF. Catalytic activity spanned a factor of four, with the most active species being the NMe catalyst, while the slowest were the GlyOMe and the AspOMe complexes. Finally, when compared to a similar set of catalysts with phenyl-substituted phosphorous groups, a clear contribution of the outer coordination sphere is seen for this family of CO2 hydrogenation catalysts.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1571505
Report Number(s):
PNNL-SA-139812
Journal Information:
Faraday Discussions, Journal Name: Faraday Discussions Vol. 215; ISSN 1359-6640; ISSN FDISE6
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (43)

Arginine-Containing Ligands Enhance H 2 Oxidation Catalyst Performance journal May 2014
Controlling Proton Delivery through Catalyst Structural Dynamics journal September 2016
Arginine-Containing Ligands Enhance H 2 Oxidation Catalyst Performance journal May 2014
Controlling Proton Delivery through Catalyst Structural Dynamics journal September 2016
The Use of Supercritical Fluids as Solvents for NMR Spectroscopy journal April 2006
The Role of Solvent and the Outer Coordination Sphere on H 2 Oxidation Using [Ni(P Cy 2 N Pyz 2 ) 2 ] 2+ : The Role of Solvent and the Outer Coordination Sphere on H journal October 2015
Electrochemical oxidation of Rh(I) to Rh(III) in rhodium(I) β-diketonato carbonyl phosphine complexes journal November 2000
Interconversion of CO2 and formic acid by bio-inspired Ir complexes with pendent bases journal August 2013
Artificial hydrogenases: biohybrid and supramolecular systems for catalytic hydrogen production or uptake journal April 2015
Solar-driven proton and carbon dioxide reduction to fuels — lessons from metalloenzymes journal April 2015
The use of supercritical fluids as solvents for NMR spectroscopy journal October 2005
Artificial Metalloenzymes: Reaction Scope and Optimization Strategies journal May 2017
Achieving Reversible H 2 /H + Interconversion at Room Temperature with Enzyme-Inspired Molecular Complexes: A Mechanistic Study journal August 2016
Reversing the Tradeoff between Rate and Overpotential in Molecular Electrocatalysts for H 2 Production journal March 2018
The Depth of Chemical Time and the Power of Enzymes as Catalysts journal December 2001
Beyond the Active Site: The Impact of the Outer Coordination Sphere on Electrocatalysts for Hydrogen Production and Oxidation journal June 2014
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation journal June 2013
Protein Design: Toward Functional Metalloenzymes journal January 2014
Structural and Functional Aspects of Metal Sites in Biology journal January 1996
The Influence of the Second and Outer Coordination Spheres on Rh(diphosphine) 2 CO 2 Hydrogenation Catalysts journal September 2014
[Ni(Et 2 PCH 2 NMeCH 2 PEt 2 ) 2 ] 2+ as a Functional Model for Hydrogenases journal January 2003
Development of Molecular Electrocatalysts for Energy Storage journal February 2014
CO 2 Hydrogenation Catalyzed by Iridium Complexes with a Proton-Responsive Ligand journal February 2015
Secondary Coordination Sphere Interactions Facilitate the Insertion Step in an Iridium(III) CO 2 Reduction Catalyst journal June 2011
Minimal Proton Channel Enables H 2 Oxidation and Production with a Water-Soluble Nickel-Based Catalyst journal November 2013
Incorporation of Pendant Bases into Rh(diphosphine) 2 Complexes: Synthesis, Thermodynamic Studies, And Catalytic CO 2 Hydrogenation Activity of [Rh(P 2 N 2 ) 2 ] + Complexes journal June 2015
Hydride Transfer from Rhodium Complexes to Triethylborane journal August 2006
Ab Initio Calculations of p K a Values of Transition-Metal Hydrides in Acetonitrile journal December 2006
Ab Initio Calculations of Thermodynamic Hydricities of Transition-Metal Hydrides in Acetonitrile journal August 2007
Designing electrochemically reversible H2 oxidation and production catalysts journal August 2018
Electrocatalytic and homogeneous approaches to conversion of CO 2 to liquid fuels journal January 2009
A proton channel allows a hydrogen oxidation catalyst to operate at a moderate overpotential with water acting as a base journal January 2014
Borinic acid catalysed peptide synthesis journal January 2015
Optimizing conditions for utilization of an H 2 oxidation catalyst with outer coordination sphere functionalities journal January 2016
The roles of the first and second coordination spheres in the design of molecular catalysts for H 2 production and oxidation journal January 2009
Second-coordination-sphere and electronic effects enhance iridium(iii)-catalyzed homogeneous hydrogenation of carbon dioxide in water near ambient temperature and pressure journal January 2012
Evaluating the role of acidic, basic, and polar amino acids and dipeptides on a molecular electrocatalyst for H 2 oxidation journal January 2017
Bio-inspired CO 2 reduction by a rhenium tricarbonyl bipyridine-based catalyst appended to amino acids and peptidic platforms: incorporating proton relays and hydrogen-bonding functional groups journal January 2017
Amino acid modified Ni catalyst exhibits reversible H 2 oxidation/production over a broad pH range at elevated temperatures journal November 2014
Design of a single protein that spans the entire 2-V range of physiological redox potentials journal December 2015
The Outer-Coordination Sphere: Incorporating Amino Acids and Peptides as Ligands for Homogeneous Catalysts to Mimic Enzyme Function journal October 2012
OLEX2 : a complete structure solution, refinement and analysis program journal January 2009
A short history of SHELX journal December 2007

Cited By (1)

Chicken fat for catalysis: a scaffold is as important for molecular complexes for energy transformations as it is for enzymes in catalytic function journal January 2019

Linked Research (1)

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY