Inter- and Intramolecular Interactions in Triptycene-Derived Bisphosphite Hydroformylation Catalysts: Structures, Energies, and Caveats for DFT-Assisted Ligand Design

The hydroformylation catalyst (L)RhH(CO)2, with a triptycene-derived bisphosphite ligand, and its iridium analogue were studied in solution, in the solid state, and computationally (DFT) in order to determine their molecular structures and to understand the equilibria between isomers. The predicted intramolecular distance of the two biphenyl side groups of these ligands strongly depends upon the treatment of inter- and intramolecular noncovalent interactions. A balanced treatment of these “weak” interactions is a prerequisite for obtaining reasonable structures and consequently also for determining relative energies of the different P-coordination modes. Low-temperature NMR studies confirm the equilibrium between axial–equatorial and equatorial–equatorial isomers in solution and have been used to estimate their relative stability in the equilibrium.

[1]  S. Grimme.  Density functional theory with London dispersion corrections , 2011 .

[2]  Marco Häser,et al.  Auxiliary basis sets to approximate Coulomb potentials , 1995 .

[3]  Filipp Furche,et al.  An efficient implementation of second analytical derivatives for density functional methods , 2002 .

[4]  H. Stoll,et al.  Energy-adjustedab initio pseudopotentials for the second and third row transition elements , 1990 .

[5]  D. Powell,et al.  Electronically Dissymmetric DIPHOS Derivatives Give Higher n:i Regioselectivity in Rhodium-Catalyzed Hydroformylation Than Either of Their Symmetric Counterparts , 1999 .

[6]  D. Truhlar,et al.  The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals , 2008 .

[7]  A. Klamt,et al.  Fast solvent screening via quantum chemistry: COSMO‐RS approach , 2002 .

[8]  F. Rominger,et al.  Phosphonite Ligand Design for Nickel‐Catalyzed 2‐Methyl‐3‐butenenitrile Isomerization and Styrene Hydrocyanation , 2010 .

[9]  P. Hofmann,et al.  Toward the Rhodium-Catalyzed Bis-Hydroformylation of 1,3-Butadiene to Adipic Aldehyde , 2011 .

[10]  A. Klamt.  Conductor-like Screening Model for Real Solvents: A New Approach to the Quantitative Calculation of Solvation Phenomena , 1995 .

[11]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[12]  K. Nozaki,et al.  New Low-Temperature NMR Studies Establish the Presence of a Second Equatorial−Apical Isomer of [(R,S)-Binaphos](CO)2RhH , 2010 .

[13]  D. Truhlar,et al.  Validation of electronic structure methods for isomerization reactions of large organic molecules. , 2011, Physical chemistry chemical physics : PCCP.

[14]  Stefan Grimme,et al.  Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction , 2006, J. Comput. Chem..

[15]  Florian Weigend,et al.  Auxiliary basis sets for main row atoms and transition metals and their use to approximate Coulomb potentials , 1997 .

[16]  J. Tomasi,et al.  Quantum mechanical continuum solvation models. , 2005, Chemical reviews.

[17]  Stefan Grimme,et al.  Does DFT-D estimate accurate energies for the binding of ligands to metal complexes? , 2011, Dalton transactions.

[18]  F. Weigend.  Accurate Coulomb-fitting basis sets for H to Rn. , 2006, Physical chemistry chemical physics : PCCP.

[19]  J. Perdew,et al.  Density-functional approximation for the correlation energy of the inhomogeneous electron gas. , 1986, Physical review. B, Condensed matter.

[20]  Luigi Cavallo,et al.  On the accuracy of DFT methods in reproducing ligand substitution energies for transition metal complexes in solution: the role of dispersive interactions. , 2012, Chemphyschem : a European journal of chemical physics and physical chemistry.

[21]  R. Ahlrichs,et al.  Geometry optimization in generalized natural internal coordinates , 1999 .

[22]  S. Grimme,et al.  A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. , 2010, The Journal of chemical physics.

[23]  S. Grimme,et al.  On the importance of the dispersion energy for the thermodynamic stability of molecules. , 2011, Chemphyschem : a European journal of chemical physics and physical chemistry.

[24]  D. Powell,et al.  Electron Withdrawing Substituents on Equatorial and Apical Phosphines Have Opposite Effects on the Regioselectivity of Rhodium Catalyzed Hydroformylation , 1997 .

[25]  F. Weigend,et al.  Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. , 2005, Physical chemistry chemical physics : PCCP.

[26]  Mohan,et al.  Erratum: Electronic response function of coupled chains of finite radius , 1986, Physical review. B, Condensed matter.

[27]  Kevin E. Riley,et al.  Performance of the DFT-D method, paired with the PCM implicit solvation model, for the computation of interaction energies of solvated complexes of biological interest. , 2007, Physical chemistry chemical physics : PCCP.

[28]  M. Head‐Gordon,et al.  Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections. , 2008, Physical chemistry chemical physics : PCCP.

[29]  D. Truhlar,et al.  Density Functional Theory for Reaction Energies: Test of Meta and Hybrid Meta Functionals, Range-Separated Functionals, and Other High-Performance Functionals , 2011 .

[30]  Hans W. Horn,et al.  ELECTRONIC STRUCTURE CALCULATIONS ON WORKSTATION COMPUTERS: THE PROGRAM SYSTEM TURBOMOLE , 1989 .

[31]  B. Sumpter,et al.  Density-functional approaches to noncovalent interactions: a comparison of dispersion corrections (DFT-D), exchange-hole dipole moment (XDM) theory, and specialized functionals. , 2011, The Journal of chemical physics.

[32]  C. Cramer,et al.  The solvation, partitioning, hydrogen bonding, and dimerization of nucleotide bases: a multifaceted challenge for quantum chemistry. , 2011, Physical chemistry chemical physics : PCCP.

[33]  D. Cremer,et al.  An efficient algorithm for the density-functional theory treatment of dispersion interactions. , 2009, The Journal of chemical physics.

[34]  F. Rominger,et al.  Highly Efficient Nickel-Catalyzed 2-Methyl-3-butenenitrile Isomerization: Applications and Mechanistic Studies Employing the TTP Ligand Family , 2011 .

[35]  K. Burke,et al.  Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] , 1997 .

[36]  Marco Häser,et al.  Auxiliary basis sets to approximate Coulomb potentials (Chem. Phys. Letters 240 (1995) 283-290) , 1995 .

[37]  S. Grimme,et al.  A thorough benchmark of density functional methods for general main group thermochemistry, kinetics, and noncovalent interactions. , 2011, Physical chemistry chemical physics : PCCP.

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

[39]  Marco Häser,et al.  Improvements on the direct SCF method , 1989 .

[40]  Giovanni Scalmani,et al.  Continuous surface charge polarizable continuum models of solvation. I. General formalism. , 2010, The Journal of chemical physics.

[41]  G. Sheldrick.  A short history of SHELX. , 2008, Acta crystallographica. Section A, Foundations of crystallography.

[42]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[43]  R. Ahlrichs,et al.  Efficient molecular numerical integration schemes , 1995 .

[44]  A. Klamt,et al.  COSMO : a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient , 1993 .

[45]  K. Goubitz,et al.  Electronic Effect on Rhodium Diphosphine Catalyzed Hydroformylation: The Bite Angle Effect Reconsidered , 1998 .

[46]  Gino A. DiLabio,et al.  Dispersion Interactions in Density‐Functional Theory , 2010 .

[47]  Filipp Furche,et al.  Efficient characterization of stationary points on potential energy surfaces , 2002 .

[48]  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.