DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Hydrogenolysis of Dinuclear PCN R Ligated Pd II μ‐Hydroxides and Their Mononuclear Pd II Hydroxide Analogues

Journal Article · · Chemistry - A European Journal
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4];  [5];  [1]; ORCiD logo [1];  [6]; ORCiD logo [7];  [8]
  1. Department of Chemistry University of Washington Box 351700 Seattle Washington 98195-1700 USA
  2. Department of Chemistry University of Pennsylvania Philadelphia PA 19104 USA
  3. Institute of Chemistry of Organometallic Compounds, ICCOM-CNR and Consorzio INSTM Via Madonna del Piano 10-50019 Sesto Fiorentino Florence Italy
  4. Kazan Federal University 420008 Kazan Russian Federation, Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS 420008 Kazan Russian Federation
  5. Università di Bari “A. Moro” Via Orabona 4 70126 Bari Italy
  6. Department of Chemistry and Chemical Biology University of New Mexico Albuquerque New Mexico 87131 USA, Advanced Materials Laboratory Sandia National Laboratories Albuquerque New Mexico 87106 USA
  7. Institute of Chemistry of Organometallic Compounds, ICCOM-CNR and Consorzio INSTM Via Madonna del Piano 10-50019 Sesto Fiorentino Florence Italy, Kazan Federal University 420008 Kazan Russian Federation, Institute of Chemistry and Processes for Energy, Environment and Health (ICPEES) UMR 7515 CNRS–University of Strasbourg (UdS) 25, rue Becquerel 67087 Strasbourg Cedex 02 France
  8. Department of Chemistry University of Washington Box 351700 Seattle Washington 98195-1700 USA, Department of Chemistry University of Pennsylvania Philadelphia PA 19104 USA

Abstract The hydrogenolysis of mono‐ and dinuclear Pd II hydroxides was investigated both experimentally and computationally. It was found that the dinuclear μ‐hydroxide complexes {[(PCN R )Pd] 2 (μ‐OH)}(OTf) (PCN H =1‐[3‐[(di‐ tert ‐butylphosphino)methyl]phenyl]‐1 H ‐pyrazole; PCN Me =1‐[3‐[(di‐ tert ‐butylphosphino)methyl]phenyl]‐5‐methyl‐1 H ‐pyrazole) react with H 2 to form the analogous dinuclear hydride species {[(PCN R )Pd] 2 (μ‐H)}(OTf). The dinuclear μ‐hydride complexes were fully characterized, and are rare examples of structurally characterized unsupported singly bridged μ‐H Pd II dimers. The {[(PCN Me )Pd] 2 (μ‐OH)}(OTf) hydrogenolysis mechanism was investigated through experiments and computations. The hydrogenolysis of the mononuclear complex (PCN H )Pd‐OH resulted in a mixed ligand dinuclear species [(PCN H )Pd](μ‐H)[(PCC)Pd] (PCC=a dianionic version of PCN H bound through phosphorus P, aryl C, and pyrazole C atoms) generated from initial ligand “rollover” C−H activation. Further exposure to H 2 yields the bisphosphine Pd 0 complex Pd[(H)PCN H ] 2 . When the ligand was protected at the pyrazole 5‐position in the (PCN Me )Pd−OH complex, no hydride formed under the same conditions; the reaction proceeded directly to the bisphosphine Pd 0 complex Pd[(H)PCN Me ] 2 . Reaction mechanisms for the hydrogenolysis of the monomeric and dimeric hydroxides are proposed.

Sponsoring Organization:
USDOE
Grant/Contract Number:
SC0018057 and DEFG02-06ER15765
OSTI ID:
1530896
Journal Information:
Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Vol. 25 Journal Issue: 42; ISSN 0947-6539
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English
Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

References (53)

Carboxylation of pincer PCP platinum methoxide complexes under formation of metalla carbonates journal January 2012
Copper polyhydrides journal December 1985
Binuclear Palladium Complexes with Bridging Hydrides. Unusual Coordination Behavior of LiBEt4 and NaBEt4 journal May 1994
Hydrogenolysis of Palladium(II) Hydroxide, Phenoxide, and Alkoxide Complexes journal November 2011
Catalytic hydrogenation of polar organic functionalities based on Ru-mediated heterolytic dihydrogen cleavage journal January 2007
The Effect of the cis-donor in pincer ligands on hydrogenolysis of Pd-OH: A DFT study journal September 2017
Linear, Redox-Active Pt6 and Pt2Pd2Pt2 Clusters journal September 2004
SIR 97: a new tool for crystal structure determination and refinement journal February 1999
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
  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n
journal May 2009
Hydride-bridged dipalladium complexes containing diphosphine ligands journal June 1997
Hydride-Bridged Pt 2 M 2 Pt 2 Hexanuclear Metal Strings (M = Pt, Pd) Derived from Reductive Coupling of Pt 2 M Building Blocks Supported by Triphosphine Ligands journal September 2012
Synthesis, Characterization, and Reactivity of N-Heterocyclic Carbene Palladium(II) Hydroxide Dimers journal September 2011
Solubility of hydrogen in 10 organic solvents at 298.15, 323.15, and 373.15 K journal July 1985
Pyrazole-Based PCN Pincer Complexes of Palladium(II): Mono- and Dinuclear Hydroxide Complexes and Ligand Rollover C–H Activation journal July 2015
Heterolytic Activation of Dihydrogen Molecule by Hydroxo-/Sulfido-Bridged Ruthenium–Germanium Dinuclear Complex. Theoretical Insights journal December 2014
Mechanisms of the H2-hydrogenation and transfer hydrogenation of polar bonds catalyzed by ruthenium hydride complexes journal December 2004
Introduction: Metal Hydrides journal June 2016
Pd(I) Phosphine Carbonyl and Hydride Complexes Implicated in the Palladium-Catalyzed Oxo Process journal August 2008
Noble metal hydroxides on carbon nonpyrophoric dry catalysts journal January 1967
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 journal July 2007
Characterization of a New Tetranuclear Cluster of Palladium, [Pd4(dppm)4(H)]— journal November 2002
The path of chemical reactions - the IRC approach journal December 1981
Linear, Redox-Active Pt6 and Pt2Pd2Pt2 Clusters journal September 2004
Binuclear Palladium Complexes Supported by Bridged Pincer Ligands journal December 2011
A set of d-polarization functions for pseudo-potential basis sets of the main group elements AlBi and f-type polarization functions for Zn, Cd, Hg journal June 1993
ORTEP -3 for Windows - a version of ORTEP -III with a Graphical User Interface (GUI) journal October 1997
Hydrogenolysis of Palladium(II) Hydroxide and Methoxide Pincer Complexes journal February 2009
Dihydrogen Complexes as Homogeneous Reduction Catalysts journal April 1998
Tetrarhena-heterocycle from the Palladium-Catalyzed Dimerization of Re 2 (CO) 8 (μ-SbPh 2 )(μ-H) Exhibits an Unusual Host–Guest Behavior journal August 2011
Recent advances in catalytic hydrogenation of carbon dioxide journal January 2011
P Csp3 P and P Csp2 P Palladium(II) Hydride Pincer Complexes: Small Structural Difference-Large Effect on Reactivity journal May 2010
Heterolysis of Dihydrogen by Silver Alkoxides and Fluorides journal June 2015
Binuclear palladium complexes with bridging hydrides. Unusual coordination behavior of LiBEt4 journal May 1991
Syntheses, structures and reactivities of [Os6Pd(CO)18(bipy)] and [{(bipy)Pd}20s3(CO)12]: Crystal and molecular structures of [{(bipy)Pd}2(μ-H)(μ-CO)][H3Os4(CO)12] and [(C4H9)4N]2[Pd2I6] journal March 1996
Soluble copper hydrides: solution behavior and reactions related to carbon monoxide hydrogenation journal December 1981
Homogeneous Hydrogenation of Carbon Dioxide journal March 1995
Selective hydride-mediated conjugate reduction of .alpha.,.beta.-unsaturated carbonyl compounds using [(Ph3P)CuH]6 journal January 1988
Effectiveness of Diffuse Basis Functions for Calculating Relative Energies by Density Functional Theory journal March 2003
Reductive Elimination of Alkanes and Arenes from [Pd 2 R 2 (μ-H)(μ-dppm) 2 ]PF 6 Complexes journal September 1999
Synthesis and structures of hydride-bridged palladium A-frame complexes journal April 2000
Syntheses and Characterization of Palladium Complexes with a Hemilabile “PCO” Pincer Ligand journal March 2011
Parst: A system of fortran routines for calculating molecular structure parameters from results of crystal structure analyses journal January 1983
Reactions of transition metal dihydrogen complexes journal December 1992
Recent Advances in Catalysis with Transition-Metal Pincer Compounds journal May 2018
A Functional Hydrogenase Model:  Reversible Interconversion of H 2 and H 2 O by a Hydroxo/Sulfido-Bridged Dinuclear Ruthenium−Germanium Complex journal February 2008
Tetrapalladium Complex with Bridging Germylene Ligands. Structural Change of the Planar Pd 4 Ge 3 Core journal November 2011
Structural variation in copper( i ) complexes with pyridylmethylamide ligands: structural analysis with a new four-coordinate geometry index, τ 4 journal January 2007
Energy-adjustedab initio pseudopotentials for the second and third row transition elements journal January 1990
The use of the Oxides of Platinum for the Catalytic Reduction of Organic Compounds. i journal June 1922
1,2-Addition of Dihydrogen across Rhodium(III)–OMe Bonds journal May 2014
Synthesis and Structure of Dinuclear Palladium(II) Complexes with Bridging Hydrido and Phosphido Ligands journal August 2000
A copper-(.mu.2-hydrogen) bond can be stronger than an intramolecular phosphorus .fwdarw. copper bond. Synthesis and structure of di-.mu.-hydridobis[.eta.2-1,1,1-tris(diphenylphosphinomethyl)ethane]dicopper journal July 1986
Methanol reduces an organopalladium(II) complex to a palladium(I) hydride. Crystallographic characterization of a hydrido-bridged palladium complex journal December 1991