Gregory R Fulmer

Publications (3)19.81 Total impact

• Article: Hydrogenolysis of palladium(II) hydroxide, phenoxide, and alkoxide complexes.

  Gregory R Fulmer, Alexandra N Herndon, Werner Kaminsky, Richard A Kemp, Karen I Goldberg
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  ABSTRACT: A series of pincer ((tBu)PCP)Pd(II)-OR complexes ((tBu)PCP = 2,6-bis(CH(2)P(t)Bu(2))C(6)H(3), R = H, CH(3), C(6)H(5), CH(2)C(CH(3))(3), CH(2)CH(2)F, CH(2)CHF(2), CH(2)CF(3)) were synthesized to explore the generality of hydrogenolysis reactions of palladium-oxygen bonds. Hydrogenolysis of the Pd hydroxide complex to generate the Pd hydride complex and water was shown to be inhibited by formation of a water-bridged, hydrogen-bonded Pd(II) hydroxide dimer. The Pd alkoxide and aryloxide complexes exhibited more diverse reactivity. Depending on the characteristics of the -OR ligand (steric bulk, electron-donating ability, and/or the presence of β-hydrogen atoms), hydrogenolysis was complicated by hydrolysis by adventitious water, a lack of reactivity with hydrogen, or a competing dissociative β-hydride abstraction reaction pathway. Full selectivity for hydrogenolysis was observed with the partially fluorinated Pd(II) 2-fluoroethoxide complex. The wide range of Pd-OR substrates examined helps to clarify the variety of reaction pathways available to late-transition-metal alkoxides as well as the conditions necessary to tune the reactivity to hydrogenolysis, hydrolysis, or dissociative β-hydride abstraction.
  Journal of the American Chemical Society 09/2011; 133(44):17713-26. · 9.91 Impact Factor
• Source

  Available from: Richard P. Muller

  Article: Hydrogenolysis of palladium(II) hydroxide and methoxide pincer complexes.

  Gregory R Fulmer, Richard P Muller, Richard A Kemp, Karen I Goldberg
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  ABSTRACT: Hydrogenolysis reactions of palladium(II) hydroxide and methoxide complexes to form water and methanol, respectively, and the corresponding palladium(II) hydride are reported. In the presence of water, 1 was found to exist in solution as a water-bridged dimer; however, kinetic studies suggest the reaction of 1 and H(2) proceeds exclusively through the hydroxide monomer to form the palladium(II) hydride and water. Computational studies suggest a four-center intramolecular proton transfer as opposed to an oxidative addition/reductive elimination pathway.
  Journal of the American Chemical Society 03/2009; 131(4):1346-7. · 9.91 Impact Factor
• Source

  Available from: Karen Goldberg

  Article: NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist

  Gregory R Fulmer, Alexander J M Miller, Nathaniel H Sherden, Hugo E Gottlieb, Abraham Nudelman, Brian M Stoltz, John E Bercaw, Karen I Goldberg
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  ABSTRACT: Tables of ^1H and ^(13)C NMR chemical shifts have been compiled for common organic compounds often used as reagents or found as products or contaminants in deuterated organic solvents. Building upon the work of Gottlieb, Kotlyar, and Nudelman in the Journal of Organic Chemistry, signals for common impurities are now reported in additional NMR solvents (tetrahydrofuran-d_8, toluene-d_8, dichloromethane-d_2, chlorobenzene-d_5, and 2,2,2-trifluoroethanol-d_3) which are frequently used in organometallic laboratories. Chemical shifts for other organics which are often used as reagents or internal standards or are found as products in organometallic chemistry are also reported for all the listed solvents.