SAS Banner
SAS Mobile Banner

Faculty Research

Moss, Robert A.

RA Moss ChemistryResearch Professor; Louis P. Hammett Professor Emeritus

Research Synopsis: Organic chemistry in aggregates, chemistry of reactive intermediates

Phone: (848) 445-2606

E-mail: rmoss@rci.rutgers.edu

 

 

 

 

Research Summary

Research in my laboratory concerns physical organic chemistry; specifically the chemistry of reactive intermediates.

The Chemistry of Reactive Intermediates

Research in my laboratory focuses on organic reaction mechanisms, specifically the chemistry of short-lived reactive intermediates, such as carbenes, carbocations, radicals, and ion pairs. We use fast spectroscopic and kinetic techniques to probe these reactions and to measure the lifetimes of the transient species. Nanosecond and picosecond laser flash photolysis are the key methodologies. Ongoing collaborations with other laboratories also permit us to use advanced computational methods, matrix isolation spectroscopy, time resolved infrared spectroscopy, and ultrafast kinetic methods to study reactive intermediates. We are thus able to follow the evolution of the transient intermediates at very short reaction times. We also develop new synthetic methods to construct precursors (mainly diazirines) for the generation of novel reactive intermediates.

Our research is supported by the National Science Foundation.

moss02

Reaction Profile for conversion of isopropoxychlorodiazirine to isopropoxychlorocarbene with AlCl3

Publications (2007-2017)

Special Issue: International Symposium on Reactive Intermediates and Unusual Molecules (ISRIUM), Hawaii, 2016. "Extremely Reactive Carbenes: Electrophiles and Nucleophiles," R.A. Moss, L. Wang, H. Cang, and K. Krogh-Jespersen J. Phys. Org. Chem. 30, e3555 (2017).

"Adventures in Reactive Intermediate Chemistry: A Perspective and Retrospective," R.A. Moss, J. Org. Chem., 82, 2307 (2017).

"Negative Activation Energies for Carbene Additions to Tetramethoxyethylene," L. Wang, R.A. Moss, and K. Krogh-Jespersen, Tetrahedron Lett., 57, 4178 (2016).

"A Half-Century Odessey in the Realm of Reactive Intermediates," R.A. Moss, Special Issue: Rosarium Philosophorum - Physical Organic Chemistry, Israel J. Chem., 56, 9 (2016).

"Two Equilibria of (N-Methyl-3-pyridinium)chlorocarbene, a Cationic Carbene," H. Cang, R.A. Moss, and K. Krogh-Jespersen, J. Phys. Chem. A, 120, 699 (2016).

"Estimation of Activation Energies for Carbene/Alkene Additions," R.A. Moss and K. Krogh-Jespersen, Tetrahedron Lett., 57, 611 (2016).   

"Nucleophilic Intermolecular Chemistry and Reactivity of Dimethylcarbene," H. Cang., R.A. Moss, and K. Krogh-Jespersen, J. Am. Chem. Soc., 137, 2730 (2015).

"Activation Parameters for Additions to Alkenes of Arylchlorocarbenes with Enhanced Electrophilicity," L. Wang, R.A. Moss, and K. Krogh-Jespersen, J. Org. Chem., 80, 7590 (2015).

"Absolute Reactivity of (N-Methyl-3-pyridinium)chlorocarbene," H. Cang, R.A. Moss, and K. Krogh-Jespersen, J. Phys. Chem. A, 119, 3556 (2015).

Special Issue: International Symposium on Reactive Intermediates and Unusual Molecules (ISRIUM), Hiroshima, 2014. R. A. Moss and A. Gudmundsdottir, Guest Editors, J. Phys. Org. Chem., 28 (No.2), 69-169 (2015).

Contemporary Carbene Chemistry, R.A. Moss and M.P. Doyle, Editors, Wiley, Hoboken, NJ (2014).

"Dependence of Activation Parameters for Phenylchlorocarbene - Alkene Additions on Alkane Solvent Chain Length," R.A. Moss, L. Wang, and K. Krogh-Jespersen, Tetrahedron Lett., 55, 6016 (2014).

"O-Ylide and Pi-Complex Formation in Reactions of a Carbene with Dibenzo and Monobenzo Crown Ethers," P.A. Hoijemberg, R.A. Moss, D.V. Feinblum, and K. Krogh-Jespersen, J. Phys. Chem A, 118, 6230 (2014).

"The 2-Norbornyl Cation - A Retrospective," R.A. Moss, J. Phys. Org. Chem., 27, 374 (2014).

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

"The Nucleophilicity of Adamantanylidene: A Hammett Study," R.A. Moss, H. Cang, and K. Krogh-Jespersen, Tetrahedron Lett., 55, 4278 (2014).

"Visualizing Carbene Equilibria," R.A. Moss, L. Wang, P.A. Hoijemberg, and K. Krogh-Jespersen, Photochem. Photobiol., 90, 287 (2014).

"Hammett Analyses of Halocarbene - Halocarbanion Equilibria," L. Wang, R.A. Moss, and K. Krogh-Jespersen, Organic Lett., 15, 2014 (2013).

"Reactivity of Chlorotrifluoromethylcarbene: Activation Parameters for Halocarbene - Alkene Addition Reactions," R.A. Moss, L. Wang, and K. Krogh-Jespersen, J. Org. Chem. 78, 11040 (2013).

"Introduction to Reactive Intermediates," R. A. Moss, Chem. Rev. 113, 6903 (2013).

"Reactive Intermediates," Chem. Rev. (Special Issue), R.A. Moss, Guest Editor, 113 (9), 6903-7342 (2013).

"Carbenic Philicity and the 'Intrinsic Reactivity Index,'" R.A. Moss and K. Krogh-Jespersen, Tetrahedron Lett., 54, 4303 (2013).

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

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

"Directly Measured Activation Parameters for the Ring Expansions of Cyclopropylhalocarbenes," Y-m. Shen, R.A. Moss, and K. Krogh-Jespersen, Organic Lett., 14, 910 (2012).

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

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

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

"Pentafluorophenylhalocarbenes," R.A. Moss, Y. Shen, L. Wang, and K. Krogh-Jespersen, Organic Lett., 13, 4752 (2011).

"Solvation and Complexation of Carbenes - A Perspective," R.A. Moss, J. Phys. Org. chem., 24, 866 (2011).

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

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

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

" 'Carbon Dichloride': Dihalocarbenes Sixty Years After Hine," R.A. Moss, J. Org. Chem. (invited Perspective), 75, 5773 (2010).

"Triplet Halocarbene Chemistry: p-Nitrophenylchlorocarbene and p-Nitrophenylbromocarbene," R.A. Moss, Z. Lu, and R.R. Sauers, Tetrahedron Lett., 51, 5940 (2010).

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

"The Generation of Diazirinone: a Computational Study," R.A. Moss and R.R. Sauers, Tetrahedron Lett., 51, 3266 (2010).

"Dihalodiazirines and the Photochemical Generation of Dihalocarbenes: New Light on Old Problems," R.A. Moss, J. Phys. Org. Chem. 23, 293 (2010).

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

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

"The Trichloromethide and Bromodichloromethide Carbanions," R.A. Moss, M. Zhang, and K. Krogh-Jespersen, Organic Lett., 11, 5702 (2009).

"Ultrafast Spectroscopy of Arylchlorodiazirines: Hammett Correlations of Excited State Lifetimes," Y. Zhang, L. Wang, R.A. Moss, and M.S. Platz, J. Am. Chem. Soc., 131, 16652 (2009).

"Innermolecular Reactions of Fluorophenylcarbene Inside a Hemicarcerand," Z. Lu, R.A. Moss, R.R. Sauers, and R. Warmuth, Organic Lett.11, 3866 (2009).

"Latent Nucleophilicity of Dichlorocarbene," R.A. Moss, M. Zhang, and K. Krogh-Jespersen, Organic Lett., 11, 1947 (2009).

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

"Ionic and Radical Fragmentations of Alkoxyhalocarbenes - A Perspective," R.A. Moss, J. Phys. Org. Chem., 22, 265 (2009).

"Activation Parameters for Additions of Ambiphilic Methoxychlorocarbene to Alkenes," R.A. Moss and M. Zhang, Organic Lett., 10, 4045 (2008).

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

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

"Chlorofluorocarbene: First UV Observation of a Dihalocarbene in Solution," R.A. Moss, J. Tian, R.R. Sauers, C. Skalit, and K. Krogh-Jespersen, Organic Lett., 9, 4053 (2007).

"Tracking "Invisible" Alkylchlorocarbenes by Their Sigma to Pi Absorptions: Dynamics and Solvent Interactions," R.A. Moss, J. Tian, R.R. Sauers, and K. Krogh-Jespersen, J. Am. Chem. Soc., 129, 10019 (2007).

"New Mechanisms Centered on Reactive Intermediates: Examples from Diazirine and Carbene Chemistry," R.A. Moss, J. Tian, G. Chu, R.R. Sauers, and K. Krogh-Jespersen, Pure Appl. Chem., 79, 993 (2007).

"SNi Fragmentations of Alkoxychlorocarbenes - A Perspective," R.A. Moss, X. Fu, and R.R. Sauers, J. Phys. Org. Chem., 20, 1 (2007).

Reviews in Reactive Intermediate Chemistry, M.S. Platz, R.A. Moss, and M. Jones, Jr., Editors, Wiley, New York, 2007.

"The Synthesis of Dichlorodiazirine and the Generation of Dichlorocarbene: Spectroscopy and Structure of Dichlorocarbene-Ylides," R.A. Moss, J. Tian, R.R. Sauers, D.H. Ess, K.N. Houk, and K. Krogh-Jespersen, J. Am. Chem. Soc, 129, 5167 (2007).

People Page

Contact Us

molecule v3

Wright-Rieman Labs
610 Taylor Road
Piscataway, NJ 08854

 

Main Office Phone:
848.445.8699