John P. Bullock

Chemistry
203 Dickinson Hall
Phone:(802) 440-4472
jbullock@bennington.edu


 

Teaching:

 
 

Fall 2012 Courses:

Chemistry 3: Organic Reactions & Mechanisms

Foundations of Physical Science

Spring 2013 Courses:

Biochemistry

Chemistry 2: Physical Principles of Chemistry

 

2013-14 Scheduled Courses:

Chemistry 1 (Fall)

Chemistry 4 (Spring)

Independent Projects (Spring)

 

Research Interests:

 

My research focuses on the elucidation of reaction pathways electrogenerated species, that is, species produced via electron transfer processes at solid electrodes. For example, some carbonyl compounds of rhenium (I), and molydenum (0) and tungsten (0), which have rich photophysical behavior and are therefore of considerable interest in the development of solar energy convesion schemes and sensing systems, can be oxidized by one-electron and frequently yield products that rapidly undergo subsequent reaction chemistry. By using techniques such as cyclic voltammetry, chronocoulometry, and spectroelectrochemistry, my students and I map the chemical steps that follow the electrode processes. One system that my system my students and I have focused on recently involves the oxidation of W(CO)5L, where L is a pyridine derivative. Subsequent to oxidation, the 17e- products undergo a rapid series of ligand substitution and disproportionation reactions, some products of which are subject to additional electron transfer, as outlined in the figure at right. Details of this particular system are presented in the poster below (click to see a larger version), which was originally presented at a recent annual meeting of Vermont EPSCoR.

In addition, I have recently been collaborating with researchers at Monash University in Australia on various aspects of Fourier-transformed ac voltammetry, especially with respect to how this powerful technique can be used to obtain more detailed information on rapid chemical reactions coupled to electrode processes. The application of this technique in the study of the electrochemical oxidation of a series of triarylphosphines was the subject of a poster I presented at the 244th National Meeting of the American Chemical Society in Philadelpia this past August; the poster can be viewed by clicking the thumbnail below.


 

Recent Papers

Bullock, J. P.; Mashkina, E.; Bond, A. M. "Activation Parameters Derived From a Temperature Dependent Large Amplitude ac Voltammetric Study of the Electrode Kinetics of the Cp2M0/+ Redox Couples (M = Fe, Co) at a Glassy Carbon Electrode" The Journal of Physical Chemistry A, 2011, 115, 6493.

Lee, C.-Y.; Bullock, J. P.; Kennedy, G. F.; Bond, A. M. "Effects of Coupled Homogeneous Chemical Reactions on the Response of Large-Amplitude AC Voltammetry: Extraction of Kinetic and Mechanistic Information by Fourier Transform Analysis of Higher Harmonic Data" The Journal of Physical Chemistry A, 2010 114, 10122.

Torriero, A. A. J.; Shiddiky, M. J. A.; Bullock, J. P.; Boas, J. F.; MacFarlane, D. R; Bond, A. M. "Electrooxidation of [(n5-C5H5)Fe(CO)2]2 As a Probe of the Nucleophilic Properties of Ionic Liquid Anions" Inorganic Chemistry, 2010, 49, 2502.

Carlson, B.; Bullock, J. P.; Hance, T. M.; Phelan, G. D. "Barometric Sensitive Coatings Based upon Osmium Complexes Dissolved in a Fluoroacrylic Polymer" Analytical Chem. 2009, 81, 262.

Carlson, B.; Eichinger, B. E.; Kaminsky, W.; Bullock, J. P.; Phelan, G. D. "Photophysical Properties, X-Ray Structures, Electrochemistry, and DFT Computational Chemistry of Osmium Complexes" Inorganic Chimica Acta, 2009, 362, 1611.

Bullock, J. P.; Carter, E.; Johnson, R.; Kennedy, A. T.; Key, S. E.; Kraft, B. J.; Saxon, D.; Underwood, P. "Reactivity of Electrochemically Generated Rhenium (II) Tricarbonyl -Diimine Complexes: A Reinvestigation of the Oxidation of Luminescent Re(CO)3( -Diimine)Cl Compounds and Related Species" Inorganic Chemistry, 2008, 47, 7880.

Johnson, R.; Madhani, H.; Bullock, J. P. "Electrochemical Oxidation of Mo(CO)4(LL) and Mo(CO)3(LL)(CH3CN): Generation, Infrared Characterization, and Reactivity of [Mo(CO)4(LL)]+ and [Mo(CO)3(LL)(CH3CN)]+" Inorg. Chim. Acta, 2007, 360, 3414.

 

 


Education & Background

Ph. D., Inorganic Chemistry, University of Minnesota, 1990

Senior Research Chemist, Air Products & Chemicals, 1990-94

Post-Doctoral Research Associate, University of Washington, 1994-95

Assistant Professor of Chemistry, Central Washington University, 1995-99

Member of the Faculty, Chemistry, The Evergreen State College, 1999-2002

 

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