Krogh-Jespersen, Karsten

Position: 
Professor Emeritus

Karsten Krogh-Jespersen

Phone: 848-445-4241

E-mail: E-mail

FAX: 732-445-5312

Office: Wright Rieman Labs A106

Mail: Chemistry & Chemical Biology, 610 Taylor Road, Piscataway, NJ 08854

 

Education Links
  • M.S. 1974, Ph.D. 1976, New York University

Research Summary

My research efforts focus on computational investigations of molecular electronic structure using ab initio and semiempirical molecular orbital techniques.

Ab initio calculation of the catalytic activation of C-H and C-F bonds by transition metals

In a DOE-funded collaboration with Professor Alan Goldman and his research group, we are using ab initio electronic structure methods to calculate thermodynamic and kinetic parameters pertaining to a number of fundamental catalytic reactions involving transition metal complexes and small molecule substrates. We are especially interested in C-X (X = H, F) bond breaking processes and in the study of oxygen atom transfer reactions. Also of interest is the accurate computation of kinetic and thermodynamic isotope effects for organometallic reactions. We hope to make such calculations into almost a "routine" tool and to provide detailed mechanistic interpretations of isotope effects for a number of prototypical - and some perhaps not so prototypical - reactions.

Semiempirical electronic structure calculations on large systems

We use semiempirical all-valence electron methods for studies of electronically excited states of large molecules. We are currently investigating a number of dimeric systems related to photosynthetic reaction centers and also some small molecular aggregates of potential interest to photovoltaic cell design. Finally, the merger of molecular orbital techniques with classical molecular mechanics/dynamics techniques for the purpose of investigating the ground and excited state properties of molecules imbedded in a condensed phase such as water or protein continue to be of interest.

Chemical Education

I have, for a number of years, mostly been involved in the teaching of General Chemistry. However, I have just returned to delivering one of my favorite courses, the introductory course in quantum chemistry for graduate students (and senior undergraduates). I am having particular fun with a number of computational assignments in this course — for additional details about this project, look at: Atomic and Molecular Structure: Chemistry 421/521


Publications

D. Laviska, C. Guan, T. J. Emge, M. Wilklow-Marnell, W. M. Brennessel, W. D. Jones, K. Krogh-Jespersen, and A. S. Goldman, “Addition of C-C and C-H Bonds by Pincer-Iridium Complexes: a Combined Experimental and Computational Study”, Dalton Trans., 43, 16354-16365 (2014).

R. A. Moss, L. Wang, and K. Krogh-Jespersen, “Dependence of activation parameters for phenylchlorocarbene-alkene additions on alkane solvent chain length”, Tetrahedron Lett., 55, 6016-6018 (2014).

P. Hoijemberg, R. A. Moss, D. V. Feinblum, and K. Krogh-Jespersen, “O-Ylide and π-Complex Formation in Reactions of a Carbene with Dibenzo and Monobenzo Crown Ethers”, J. Phys. Chem. A, 118, 6231-6238 (2014).

R. A. Moss, H. Cang, and K. Krogh-Jespersen, “The nucleophilicity of adamantanylidene: a Hammett study”, Tetrahedron Lett., 55, 4278-4280, (2014).

J. D. Hackenberg, S. Kundu, T. J. Emge, K. Krogh-Jespersen, and A. S. Goldman, “Acid-Catalyzed Oxidative Addition of a C-H Bond to a Square Planar d8 Iridium Complex”, J. Am. Chem. Soc., 136, 8891-8894 (2014).

C. Cheng, B. G. Kim, D. Guironnet, M. Brookhart, C. Guan, D. Y. Wang, K. Krogh-Jespersen, and A. S. Goldman, “Synthesis and Characterization of Carbazolide-based Iridium PNP Pincer Complexes. Mechanistic and Computational Investigation of Alkene Hydrogenation: Evidence for an Ir(III)/Ir(V)/Ir(III) Catalytic Cycle”, J. Am. Chem. Soc. 136, 6672-6683 (2014).

Q. Cao, G. Gor, K. Krogh-Jespersen, and L. Khriachtchev, “Non-Covalent Interactions of Nitrous Oxide with Aromatic Compounds: Spectroscopic and Computational Evidence for the Formation of 1:1 Complexes”, J. Chem. Phys., 140, 144304 (2014).

R. A. Moss, L. Wang, and K. Krogh-Jespersen, “The Nucleophilicity of a Dialkylcarbene: Unusual Activation Parameters for Additions of Adamantanylidene to Simple Alkenes”, J. Am. Chem. Soc., 136, 4885-4888 (2014).

R. A. Moss, L. Wang, P. A. Hoijemberg, and K. Krogh-Jespersen, “Visualizing Carbene Equilibria”, Photochem. Photobiol. A: Chem., 90, 287-293 (2014) (Invited Review; also featured as a Highlight paper).

J. Hackenberg, K. Krogh Jespersen, and A. S. Goldman, “Activation of C-O and C-F Bonds by Pincer-iridium Complexes”, pp. 39-58 in “Advances in Organometallic Chemistry and Catalysis: The Silver/Gold Jubilee International Conference on Organometallic Chemistry Celebratory Book,” A. J. L. Pombeiro, Ed.; John Wiley & Sons, Hoboken, NJ (2013).

R. A. Moss, L. Wang, and K. Krogh-Jespersen, “The Reactivity of Chlorotrifluoromethylcarbene: Activation Parameters for Halocarbene-Alkene Addition Reactions”, J. Org. Chem., 78, 11040-11044 (2013). http://dx.doi.org/10.1021/jo402058k

M. C. Haibach, C. Guan, D. Y. Wang, B. Li, N. Lease, A. Steffens, K. Krogh-Jespersen, and A. S. Goldman, “Olefin Hydroaryloxylation Catalyzed by Pincer Iridium Complexes”, J. Am. Chem. Soc., 135, 15062-15070 (2013). http://dx.doi.org/10.1021/ja404566v

M. C. Haibach, D. Y. Wang, T. J. Emge, K. Krogh-Jespersen, and A. S. Goldman, “(POP)Rh Pincer Hydride Complexes: Unusual Reactivity and Selectivity in Oxidative Addition and Olefin Insertion Reactions”, Chem. Sci., 4, 3683-3692 (2013).

R. A. Moss and K. Krogh-Jespersen, “Carbenic philicity and the “intrinsic reactivity index” Tetrahedron Lett., 54, 4303-4305 (2013).

L. Wang, R. A. Moss, and K. Krogh-Jespersen, “Hammett Analysis of Halocarbene-Halocarbanion Equilibria” Org. Lett. 15, 2014-2017 (2013)

S. Kundu, J. Choi, Y. Choliy, T. J. Emge, K. Krogh-Jespersen, and A. S. Goldman, "Oxidative Addition of Ether, Ester and Tosylate C(sp3)-O Bonds to an Iridium Complex, Initiated by Oxidative Addition of C-H Bonds. Experimental and Computational Studies", J. Am. Chem. Soc., 135, 5127-5143 (2013).

L. Wang, R. A. Moss, and K. Krogh-Jespersen, “Directly Observed Halocarbene – Halocarbanion Equilibration” J. Am. Chem. Soc., 134, 17459-17461 (2012).

S. Biswas, Z. Huang, Y. Choliy, D. Y. Wang, M. Brookhart, K. Krogh-Jespersen, and A. S. Goldman, "Olefin Isomerization by Iridium Pincer Catalysts. Experimental Evidence for an η3-Allyl Pathway and an Unconventional Mechanism Predicted by DFT Calculations", J. Am. Chem. Soc., 134, 13276-13295 (2012).

F. Hasanayn, P. Achord, P. Braunstein, H. J. Magnier, K. Krogh-Jespersen, and A.S. Goldman, “Theoretical Structure-Reactivity Study of Ethylene Insertion into Nickel-Alkyl Bonds. A Kinetically Significant and Unanticipated Role of trans Influence in Determining Agostic Bond Strengths”, Organometallics, 31, 4680-4692 (2012).

P. Hoijemberg, R. A. Moss, and K. Krogh-Jespersen, “Solvent Polarity Effects on Carbene/Ether-O-Ylide Equilibria”, J. Phys. Chem. A, 116, 4745-4750 (2012).

Y. Shen, R. A. Moss, and K. Krogh-Jespersen, “Directly Measured Activation Parameters for the Ring Expansions of Cyclopropyl-halocarbenes”, Org. Lett., 14, 910-913 (2012).

M. Zhang, R. A. Moss, J. Thompson, and K. Krogh-Jespersen, "Evolution of Structure and Reactivity in a Series of Iconic Carbenes", J. Org. Chem, 77, 843-850 (2012). Published as a Featured Article.

P. Hoijemberg, R. A. Moss, and K. Krogh-Jespersen, “Reversible O-Ylide Formation in Carbene/Ether Reactions”, J. Phys. Chem. A, 116, 358-363 (2012).

Z. Lu, R. A. Moss, R. Warmuth, and K. Krogh-Jespersen, “A Transient Innermolecular Carbene-Hemicarcerand Complex of Fluorophenylcarbene” J. Phys. Chem. A, 115, 13799-13803 (2011).

R. A. Moss, Y. Shen, L. Wang, and K. Krogh-Jespersen, “Pentafluorophenylhalocarbenes”, Org. Lett., 13, 4752-4754 (2011).

L. Wang, R. A. Moss, and K. Krogh-Jespersen, “Trimethoxybenzene Complexes of Pentafluorophenylchlorocarbene” J. Phys. Chem. A, 115, 8113-8118 (2011).

J. Choi, D. Y. Wang, S. Kundu, Y. Choliy, T. J. Emge, K. Krogh-Jespersen, and A. S. Goldman, "Oxidative Addition of C(sp3)-F Bonds to Iridium via Initial C-H Bond Activation", Science, 332, 1545-1548 (2011). Commentary at http://www.rsc.org/chemistryworld/News/2011/June/23061103.asp and http://videnskab.dk/miljo-naturvidenskab/en-af-verdens-staerkeste-kulstofbindinger-besejret

L. Wang, R. A. Moss, J. Thompson, and K. Krogh-Jespersen, “Hammett Analysis of a Family of Carbene - Carbene Complex Equilibria", Org. Lett., 13, 1198-1201 (2011).

Y. Issa, K. Krogh Jespersen, and S. S. Isied, "Conformational Dependence of Electronic Coupling Across Peptide Bonds: Ramachandran Map”, J. Phys. Chem. C, 114, 20809-20812 (2010).

R. A. Moss, L. Wang, C. M. Odorisio, and K. Krogh-Jespersen, “A Carbene - Carbene Complex Equilibrium", J. Am. Chem. Soc., 132, 10677-10679 (2010).

R. A. Moss, M. Zhang, and K. Krogh-Jespersen, "The Nucleophilic Reactivity of Fluoromethoxycarbene", Org. Lett., 12, 3476-3479 (2010).

R. A. Moss, L. Wang, C. M. Odorisio, and K. Krogh-Jespersen, “Complexation of Dichlorocarbene by Methylanisoles”, Tetrahedron Lett., 51, 1467-1470 (2010).

T. J. Hebden, K. I. Goldberg, D. M. Heinekey, X. Zhang, T. J. Emge, A. S. Goldman, and K. Krogh-Jespersen, “Dihydrogen/Dihydride or Tetrahydride? An Experimental and Computational Investigation of Pincer Iridium Polyhydrides”, Inorg. Chem., 49, 1733-1742 (2010).

K. Krogh-Jespersen, M. D. Romanelli, J. Melman, T. J. Emge, and J. G. Brennan, “Covalent Bonding and the Trans Influence in Lanthanide Compounds”, Inorg. Chem., 49, 552-560 (2010).

R. A. Moss, L. Wang, C. M. Odorisio, M. Zhang, and K. Krogh-Jespersen, “The Solvation of Dichlorocarbene: Complexation with Aryl Ethers”, J. Phys. Chem. A, 114, 209-217 (2010).

R. A. Moss, M. Zhang, and K. Krogh-Jespersen, “The Trichloromethide and Bromodichloromethide Carbanions”, Org. Lett., 11, 5702-5704 (2009).

J. Choi, Y. Choliy, X. Zhang, T. J. Emge, K. Krogh-Jespersen, and A. S. Goldman, “Cleavage of C(sp3)-O Bonds via Oxidative Addition of C-H Bonds”, J. Am. Chem. Soc., 131, 15627-15629 (2009).

S. Kundu, Y. Choliy, G. Zuo, R. Ahuja, T. J. Emge, R. Warmuth, M. Brookhart, K. Krogh-Jespersen, and A. S. Goldman, “Rational Design and Synthesis of Highly Active Pincer-Iridium Catalysts for Alkane Dehydrogenation”, Organometallics, 28, 5432-5444 (2009).

R. A. Moss, M. Zhang, and K. Krogh-Jespersen, “Latent Nucleophilicity of Dichlorocarbene”, Org. Lett., 11, 1947-1950 (2009).

R. A. Moss, L. Wang, and K. Krogh-Jespersen, “A New Synthesis of Difluorodiazirene and the Absolute Reactivity of Difluorocarbene”, J. Am. Chem. Soc., 131, 2128-2130 (2009).

E. Pelczar, T. J. Emge, K. Krogh Jespersen, and A. S. Goldman, “Iron Containing PNP-Pincer Complexes with Unusual Structural and Spectrocopic Features”, Organometallics, 27, 5759-5767 (2008).

K. Krogh-Jespersen, R. T. Stibrany, E. John, J. D. Westbrook, T. J. Emge, M. J. Clarke, J. A. Potenza, and H. J. Schugar, “Solid- State Changes in Ligand-to-Metal-Charge-Transfer Spectra of (NH3)5RuIII(2,4-dihydroxybenzoate) and (NH3)5RuIII(xanthine) Chromophores”, Inorg. Chem., 47, 9813-9827 (2008).

R. Ghosh, T. J. Emge, K. Krogh Jespersen, and A. S. Goldman, “Combined Experimental and Computational Studies on Carbon-Carbon Reductive Elimination from Bis(hydrocarbyl)Complexes of (PCP)Ir”, J. Am. Chem. Soc., 130, 11317-11327 (2008).

R. A. Moss, L. Wang, E. Weintraub, and K. Krogh-Jespersen, “The Solvation of Carbenes: Π and Ylidic Complexes of p-Nitrophenylchlorocarbene”, J. Phys. Chem. A, 112, 4651-4659 (2008).

R. A. Moss, L. Wang, M. Zhang, C. Skalit,and K. Krogh-Jespersen, “Enthalpy vs Entropy in Chlorocarbene/Alkene Addition Reactions”, J. Am. Chem. Soc., 130, 5634-5635 (2008).

J.-S. Chen, K. Krogh-Jespersen, and J. G. Khinast, “Base- and Ligand-Free Heterogeneously Catalyzed Homocoupling of Arylboronic Acids”, J. Mol. Cat. A: Chemical, 285, 14-19 (2008).


Research Area(s): 
Physical Chemistry