Molecular Mechanics Force Field for Octahedral Organometallic Compounds with Inclusion of the Trans Influence.

Efficient calculation of the properties of metal-containing complexes relevant to catalysis is of major interest for better characterizing and optimizing the catalysts. For this, a new force field, called VALBOND-TRANS here, is proposed. It is based on the existing VALBOND force field of Landis and co-workers, extended by adding terms that account for electronic effects such as the trans influence of ligands on bond lengths and relative energies. Parameters and results for model octahedral complexes of Ru, Os, Rh, and Ir are determined and discussed. The model is then applied to the study of reactive intermediates involved in asymmetric hydrogenation catalyzed by iridium complexes with chiral phosphinooxazolines (PHOX) ligands. The new force field explores and capitalizes on the separation of electronic and steric effects on the stability of different diastereomers and reproduces DFT results which are consistent with experimental observations.

[1]  A. Pfaltz,et al.  Enantioselective Hydrogenation of Olefins with Iridium-Phosphanodihydrooxazole Catalysts. , 1998, Angewandte Chemie.

[2]  Peter Comba,et al.  Molecular mechanics and the Jahn-Teller effect , 1994 .

[3]  Clark R. Landis,et al.  Molecular Mechanics Force Fields for Modeling Inorganic and Organometallic Compounds , 2007 .

[4]  Markus Meuwly,et al.  Atomistic Simulation of Adiabatic Reactive Processes Based on Multi-State Potential Energy Surfaces. , 2008, Journal of chemical theory and computation.

[5]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[6]  P. Comba.  The relation between ligand structures, coordination stereochemistry, and electronic and thermodynamic properties , 1993 .

[7]  Thomas Strassner,et al.  Evaluation of Functionals O3LYP, KMLYP, and MPW1K in Comparison to B3LYP for Selected Transition-Metal Compounds. , 2005, Journal of chemical theory and computation.

[8]  M. Meuwly,et al.  A combined experimental and computational study of dihydrido(phosphinooxazoline)iridium complexes. , 2004, Journal of the American Chemical Society.

[9]  B. Coe,et al.  Trans-effects in octahedral transition metal complexes , 2000 .

[10]  F. Allen.  The Cambridge Structural Database: a quarter of a million crystal structures and rising. , 2002, Acta crystallographica. Section B, Structural science.

[11]  T. Norrby,et al.  Molecular Mechanics (MM3) Parameters for Ruthenium(II)-Polypyridyl Complexes. , 1998, Inorganic chemistry.

[12]  W. L. Jorgensen,et al.  Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids , 1996 .

[13]  Peter Comba,et al.  Inorganic Molecular Mechanics , 1996 .

[14]  K. Burgess,et al.  Catalytic homogeneous asymmetric hydrogenations of largely unfunctionalized alkenes. , 2005, Chemical reviews.

[15]  W. R. Wadt,et al.  Ab initio effective core potentials for molecular calculations , 1984 .

[16]  F. Weinhold,et al.  Natural population analysis , 1985 .

[17]  Robert J Deeth.  Comprehensive molecular mechanics model for oxidized type I copper proteins: active site structures, strain energies, and entatic bulging. , 2007, Inorganic chemistry.

[18]  P. Comba,et al.  MOLECULAR MECHANICS CALCULATIONS OF TRANSITION-METAL COMPLEXES , 1992 .

[19]  U. Singh,et al.  A NEW FORCE FIELD FOR MOLECULAR MECHANICAL SIMULATION OF NUCLEIC ACIDS AND PROTEINS , 1984 .

[20]  R. Pearson.  Antisymbiosis and the trans effect , 1973 .

[21]  A. Pfaltz,et al.  Iridium-Catalyzed Enantioselective Hydrogenation of Olefins , 2003 .

[22]  Robert J. Deeth,et al.  The ligand field molecular mechanics model and the stereoelectronic effects of d and s electrons , 2001 .

[23]  Per-Ola Norrby,et al.  Development of a Q2MM Force Field for the Asymmetric Rhodium Catalyzed Hydrogenation of Enamides. , 2008, Journal of chemical theory and computation.

[24]  A. Pfaltz,et al.  Iridium-catalyzed asymmetric hydrogenation of olefins. , 2007, Accounts of chemical research.

[25]  Alexander D. MacKerell,et al.  All-atom empirical potential for molecular modeling and dynamics studies of proteins. , 1998, The journal of physical chemistry. B.

[26]  Nohad Gresh,et al.  Inclusion of the ligand field contribution in a polarizable molecular mechanics: SIBFA‐LF , 2003, J. Comput. Chem..

[27]  W. Steele.  Chapter 6. The thermochemistry of organometallic compounds , 1974 .

[28]  P. Andersson,et al.  Ir-catalysed asymmetric hydrogenation: Ligands, substrates and mechanism. , 2006, Chemistry.

[29]  Clark R. Landis,et al.  Valence Bond Concepts Applied to the Molecular Mechanics Description of Molecular Shapes. 2. Applications to Hypervalent Molecules of the P-Block , 1993 .

[30]  Peter L. Freddolino,et al.  Molecular dynamics simulations of the complete satellite tobacco mosaic virus. , 2006, Structure.

[31]  M. Zimmer,et al.  BIOINORGANIC MOLECULAR MECHANICS , 1995 .

[32]  Peter Comba,et al.  Inorganic and bioinorganic molecular mechanics modeling—the problem of the force field parameterization , 2003 .

[33]  J. Boeyens,et al.  Molecular mechanics: theoretical basis, rules, scope and limits , 2001 .

[34]  Per-Ola Norrby,et al.  Deriving force field parameters for coordination complexes , 2001 .

[35]  M. Karplus,et al.  CHARMM: A program for macromolecular energy, minimization, and dynamics calculations , 1983 .

[36]  Clark R. Landis,et al.  VALENCE BOND CONCEPTS APPLIED TO THE MOLECULAR MECHANICS DESCRIPTION OF MOLECULAR SHAPES. 3. APPLICATIONS TO TRANSITION METAL ALKYLS AND HYDRIDES , 1998 .

[37]  W. Goddard,et al.  UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations , 1992 .