Hydrogen elimination reactivity of ruthenium pincer hydride complexes: a DFT study

The pincer effect is explained for various pincer hydride complexes, differing in the donor atoms, using activation barriers, and MESP parameters.

[1]  C. Suresh,et al.  Quantification of Thermodynamic Hydridicity of Hydride Complexes of Mn, Re, Mo, and W Using the Molecular Electrostatic Potential. , 2017, The journal of physical chemistry. A.

[2]  A. Albinati,et al.  Synthesis of an Optically Active Platinum(II) Complex Containing a New Terdentate P-C-P Ligand and Its Catalytic Activity in the Asymmetric Aldol Reaction of Methyl Isocyanoacetate. X-ray Crystal Structure of [2,6-Bis[(1'S,2'S)-1'-(diphenylphosphino)-2',3'-O-isopropylidene-2',3'-dihydroxypropyl]phen , 1994 .

[3]  Charity Flener Lovitt,et al.  Donor–Acceptor Properties of Bidentate Phosphines. DFT Study of Nickel Carbonyls and Molecular Dihydrogen Complexes , 2012 .

[4]  C. Suresh,et al.  Assessment of stereoelectronic effects in grubbs first-generation olefin metathesis catalysis using molecular electrostatic potential , 2011 .

[5]  D. M. Grove,et al.  Versatile N,C,N Coordiantion Behaviour of a Monoanionic Aryldiamine Ligand in Ruthenium(II) Complexes: Syntheses and Crystal structures of [RuII{C6H3(CH2NMe2)2-2,6}X(L)](L=Norbornadiene, X=Cl, SO3CF3; L=PPh3, X=I) and [RuII{C6H3(CH2NMe2)2-2,6}(2,2':6',2'-terpyridine)]Cl , 1996 .

[6]  V. Barone,et al.  Quantum Calculation of Molecular Energies and Energy Gradients in Solution by a Conductor Solvent Model , 1998 .

[7]  C. Jensen,et al.  Oxidative Addition of Water by an Iridium PCP Pincer Complex: Catalytic Dehydrogenation of Alkanes by IrH(OH){C6H3-2,6-(CH2PBut2)2} , 2001 .

[8]  Natalie Fey The contribution of computational studies to organometallic catalysis: descriptors, mechanisms and models. , 2010, Dalton transactions.

[9]  J. Yang,et al.  13C NMR Spectroscopic Determination of Ligand Donor Strengths Using N-Heterocyclic Carbene Complexes of Palladium(II) , 2009 .

[10]  Kazunari Yoshizawa,et al.  Metal-ligand cooperation in H2 production and H2O decomposition on a Ru(II) PNN complex: the role of ligand dearomatization-aromatization. , 2009, Journal of the American Chemical Society.

[11]  P. Nelson,et al.  Review: Pincer ligands—Tunable, versatile and applicable , 2017 .

[12]  Dani,et al.  Hydrogen-Transfer Catalysis with Pincer-Aryl Ruthenium(II) Complexes. , 2000, Angewandte Chemie.

[13]  C. Bannwarth,et al.  Consistent structures and interactions by density functional theory with small atomic orbital basis sets. , 2015, The Journal of chemical physics.

[14]  Keiji Morokuma,et al.  Ab initio Molecular Orbital Studies of Catalytic Elementary Reactions and Catalytic Cycles of Transition-Metal Complexes , 1991 .

[15]  C. Richards,et al.  Cationic [2,6-Bis(2‘-oxazolinyl)phenyl]palladium(II) Complexes: Catalysts for the Asymmetric Michael Reaction , 2000 .

[16]  C. Jensen,et al.  High yield olefination of a wide scope of aryl chlorides catalyzed by the phosphinito palladium PCP pincer complex: [PdCl{C6H3(OPPri2)2-2,6}] , 2000 .

[17]  Cunyuan Zhao,et al.  When Bifunctional Catalyst Encounters Dual MLC Modes: DFT Study on the Mechanistic Preference in Ru-PNNH Pincer Complex Catalyzed Dehydrogenative Coupling Reaction , 2017 .

[18]  A. B. P. Lever,et al.  Electrochemical parametrization of metal complex redox potentials, using the ruthenium(III)/ruthenium(II) couple to generate a ligand electrochemical series , 1990 .

[19]  Artur Michalak,et al.  Natural orbitals for chemical valence as descriptors of chemical bonding in transition metal complexes , 2007, Journal of molecular modeling.

[20]  C. Suresh,et al.  Use of molecular electrostatic potential at the carbene carbon as a simple and efficient electronic parameter of N-heterocyclic carbenes. , 2010, Inorganic chemistry.

[21]  R. Crabtree,et al.  Key factors in pincer ligand design. , 2018, Chemical Society reviews.

[22]  Peter Politzer,et al.  Chemical Applications of Atomic and Molecular Electrostatic Potentials: "Reactivity, Structure, Scattering, And Energetics Of Organic, Inorganic, And Biological Systems" , 2013 .

[23]  C. Jensen,et al.  A highly active alkane dehydrogenation catalyst: stabilization of dihydrido rhodium and iridium complexes by a P–C–P pincer ligand , 1996 .

[24]  David Milstein,et al.  Cyclometalated phosphine-based pincer complexes: mechanistic insight in catalysis, coordination, and bond activation. , 2003, Chemical reviews.

[25]  M. Albrecht,et al.  Detection of ppm quantities of gaseous SO2 by o9rganoplatinum dendritic sites immobilised on a quartz microbalance. , 2001, Chemical communications.

[26]  M. Page,et al.  Pyridine-2,6-bis(thioether) (SNS) complexes of ruthenium as catalysts for transfer hydrogenation , 2010 .

[27]  K. Takeuchi,et al.  Synthesis and characterization of ruthenium complexes which utilize a new family of terdentate ligands based upon 2,6-bis(pyrazol-1-yl)pyridine , 1993 .

[28]  Z. Lai,et al.  Enhanced Reactivities toward Amines by Introducing an Imine Arm to the Pincer Ligand: Direct Coupling of Two Amines To Form an Imine Without Oxidant , 2012 .

[29]  J. Loch,et al.  Computed ligand electronic parameters from quantum chemistry and their relation to Tolman parameters, Lever parameters, and Hammett constants. , 2001, Inorganic chemistry.

[30]  Yehoshoa Ben‐David,et al.  Facile Conversion of Alcohols into Esters and Dihydrogen Catalyzed by New Ruthenium Complexes , 2005 .

[31]  S. Draper,et al.  Palladium bis(phosphinite) ‘PCP’-pincer complexes and their application as catalysts in the Suzuki reaction , 2000 .

[32]  Xinzheng Yang,et al.  Trigger mechanism for the catalytic hydrogen activation by monoiron (iron-sulfur cluster-free) hydrogenase. , 2008, Journal of the American Chemical Society.

[33]  C. Suresh,et al.  Pincer Ligand Modifications To Tune the Activation Barrier for H2 Elimination in Water Splitting Milstein Catalyst. , 2015, Inorganic chemistry.

[34]  C. Suresh,et al.  Quantification and classification of substituent effects in organic chemistry: a theoretical molecular electrostatic potential study. , 2016, Physical chemistry chemical physics : PCCP.

[35]  D. Gusev Donor Properties of a Series of Two-Electron Ligands , 2009 .

[36]  O. Eisenstein,et al.  C-H bond activation in transition metal species from a computational perspective. , 2010, Chemical reviews.

[37]  G. Koten,et al.  Diaminoarylnickel(II) “Pincer” Complexes: Mechanistic Considerations in the Kharasch Addition Reaction, Controlled Polymerization, and Dendrimeric Transition Metal Catalysts , 1998 .

[38]  C. Cramer,et al.  Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. , 2009, The journal of physical chemistry. B.

[39]  Bai Amutha Anjali,et al.  Correlation and Prediction of Redox Potentials of Hydrogen Evolution Mononuclear Cobalt Catalysts via Molecular Electrostatic Potential: A DFT Study. , 2016, The journal of physical chemistry. A.

[40]  D. Milstein,et al.  Metal-ligand cooperation by aromatization-dearomatization: a new paradigm in bond activation and "green" catalysis. , 2011, Accounts of chemical research.

[41]  D. Milstein,et al.  Bond activation and catalysis by ruthenium pincer complexes. , 2014, Chemical reviews.

[42]  G. Koten,et al.  Synthesis and Characterization of the Bis-Cyclometalating Ligand 3,3‘,5,5‘-Tetrakis[(dimethylamino)methyl]biphenyl and Its Use in the Preparation of Bimetallic M(II), M(IV) (M = Pt, Pd), and Mixed-Valence Pt(II)−Pt(IV) Complexes via a Dilithio-Derivative. Crystal Structure of the Pd Dimer [ClPd{2,6- , 1998 .

[43]  Cherumuttathu H. Suresh,et al.  Water Splitting Promoted by a Ruthenium(II) PNN Complex: An Alternate Pathway through a Dihydrogen Complex for Hydrogen Production , 2011 .

[44]  Bai Amutha Anjali,et al.  Interpreting Oxidative Addition of Ph–X (X = CH3, F, Cl, and Br) to Monoligated Pd(0) Catalysts Using Molecular Electrostatic Potential , 2017, ACS omega.

[45]  Siwei Shu,et al.  Catalyzed or non-catalyzed: chemoselectivity of Ru-catalyzed acceptorless dehydrogenative coupling of alcohols and amines via metal–ligand bond cooperation and (de)aromatization , 2019, Catalysis Science & Technology.

[46]  D. MacMillan,et al.  Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis. , 2013, Chemical reviews.

[47]  J. Harvey,et al.  On the accuracy of density functional theory in transition metal chemistry , 2006 .

[48]  S. Niu,et al.  Theoretical studies on reactions of transition-metal complexes. , 2000, Chemical reviews.

[49]  C. A. Tolman,et al.  Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis , 1977 .

[50]  K. Kirchner,et al.  Modularly designed transition metal PNP and PCP pincer complexes based on aminophosphines: synthesis and catalytic applications. , 2008, Accounts of chemical research.

[51]  Chunyu Song,et al.  Catalytic mechanisms of direct pyrrole synthesis via dehydrogenative coupling mediated by PNP-Ir or PNN-Ru pincer complexes: crucial role of proton-transfer shuttles in the PNP-Ir system. , 2014, Journal of the American Chemical Society.

[52]  David Milstein,et al.  Consecutive Thermal H2 and Light-Induced O2 Evolution from Water Promoted by a Metal Complex , 2009, Science.

[53]  Y. Diskin‐Posner,et al.  PNS-Type Ruthenium Pincer Complexes , 2012 .

[54]  Peter Politzer,et al.  The fundamental nature and role of the electrostatic potential in atoms and molecules , 2002 .

[55]  K. Itoh,et al.  Chiral Ruthenium(II)-Bis(2-oxazolin-2-yl)pyridine Complexes. Asymmetric Catalytic Cyclopropanation of Olefins and Diazoacetates. , 1995 .

[56]  N. Hazari,et al.  Selective conversion of glycerol to lactic acid with iron pincer precatalysts. , 2015, Chemical communications.

[57]  Walter Kohn,et al.  Nobel Lecture: Electronic structure of matter-wave functions and density functionals , 1999 .

[58]  D. Milstein,et al.  Direct synthesis of imines from alcohols and amines with liberation of H2. , 2010, Angewandte Chemie.

[59]  Nicklas Selander,et al.  Catalysis by palladium pincer complexes. , 2011, Chemical reviews.

[60]  M. Albrecht,et al.  Platinum Group Organometallics Based on "Pincer" Complexes: Sensors, Switches, and Catalysts. , 2001, Angewandte Chemie.

[61]  H. Rozenberg,et al.  Osmium-mediated C--H and C--C bond cleavage of a phenolic substrate: p-quinone methide and methylene arenium pincer complexes. , 2007, Chemistry.

[62]  K. Kirchner,et al.  Stereospecific and reversible CO binding at iron pincer complexes. , 2008, Angewandte Chemie.

[63]  D. Milstein,et al.  Highly Active Pd(II) PCP-Type Catalysts for the Heck Reaction , 1997 .

[64]  A. Lledós,et al.  Transition metal polyhydrides: from qualitative ideas to reliable computational studies. , 2000, Chemical reviews.

[65]  C. Moulton,et al.  Transition metal–carbon bonds. Part XLII. Complexes of nickel, palladium, platinum, rhodium and iridium with the tridentate ligand 2,6-bis[(di-t-butylphosphino)methyl]phenyl , 1976 .

[66]  B. Wood,et al.  Influence of DFT Functionals and Solvation Models on the Prediction of Far-Infrared Spectra of Pt-Based Anticancer Drugs: Why Do Different Complexes Require Different Levels of Theory? , 2019, ACS omega.

[67]  K. Kirchner,et al.  A Modular Approach to Achiral and Chiral Nickel(II), Palladium(II), and Platinum(II) PCP Pincer Complexes Based on Diaminobenzenes , 2006 .

[68]  C. Suresh,et al.  Designing metal hydride complexes for water splitting reactions: a molecular electrostatic potential approach. , 2014, Dalton transactions.

[69]  G. Giambastiani,et al.  Cationic Group-IV pincer-type complexes for polymerization and hydroamination catalysis. , 2013, Dalton transactions.

[70]  D. M. Grove,et al.  New arylruthenium(II) complexes of the P,C,P'-Coordinating terdentate monoanionic aryl ligands [C6H2(CH2PPh2)2-2,6-R-4]- (PCP-R-4; R = Ph, H). Synthesis of 16-electron species [RuIIX(PCP-R-4)(PPh3)] (X = Cl, L, OTf) and their reactivity toward the neutral terdentate N-donor ligand 2,2':6',2''-terpyr , 1996 .

[71]  C. Suresh,et al.  Assessment of the electron donor properties of substituted phenanthroline ligands in molybdenum carbonyl complexes using molecular electrostatic potentials , 2018 .

[72]  A. Lever ELECTROCHEMICAL PARAMETRIZATION OF RHENIUM REDOX COUPLES , 1991 .