J. Michael McBride
homepage:http://www.chem.yale.edu/faculty/mcbride.html
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Description

Research

In much of traditional organic chemistry, experiment involves molecules in solution, and theory involves isolated molecules in the gas phase. Most organic substances in our daily lives, however, whether natural or synthetic, are solids. These range from pharmaceuticals to rocket fuels, from clothing to antibody-antigen complexes, from kidney stones to photoresists. Our research uses physical-organic chemistry to understand and control the chemical reactivity and physical properties of organic solids. Research.

We study single crystals. Because the molecules in a crystal have identical conformations, environments, and orientations, their chemical and physical behavior is extraordinarily uniform. Furthermore, powerful techniques are available for determining and interpreting the detailed behavior of molecules in single crystals. Beyond the standard organic techniques for preparing and analyzing samples we have relied heavily on x-ray diffraction, low-temperature ESR and FTIR spectroscopy, and computer modeling, and most recently on atomic force microscopy (AFM). With an oriented single crystal one can see individual functional groups with polarized spectroscopy and feel them with AFM.

Currently we work in three areas: detailed study of reaction mechanisms in photolyzed crystals to find how, and why, they differ from those in solution; study of how changes in molecular structure influence the physical properties of organic solids; and primarily on study of crystal growth and what it reveals about molecular recognition.

Our previous work on reaction mechanisms in crystalline diacyl peroxides has provided a set of experimental tools and an understanding of simple processes that we now have applied to much more complex systems. John Toscano observed as many as 60 reactive intermediates on three independent pathways in a single crystal of an important nitramine explosive, whose decomposition mechanism had remained unknown after half a century of intensive study.

We have discovered novel reaction intermediates. In one nitramine crystal Lev Ryzhkov measured a “bond strength” of only 10 millicalories/mole between radicals separated by 10Å; and in another Matthew Weinschenk found a new reactive intermediate, Y-shaped N2O2. Randy Carter explained the formation of a curious molecular diradical in crystalline decanoyl peroxide (DP). When two CO2 molecules are expelled by photolyzing the top molecule in Figure 1, the resulting nonyl radicals each abstract an α-hydrogen from the molecule below. In undecanoyl peroxide (UP) crystals, where each chain is one carbon longer, the adjacent molecules are too far away and alternative products form.

We are particularly interested in contributing to a new kind of rational organic synthesis, whose goal is to assemble not molecules from atoms, but crystals from molecules. Controlling crystal growth is a challenging goal of vital commercial and biomedical importance. Steve Bertman and Bart Kahr developed a technique using the polarizing microscope to read out the record of crystal growth stored in many “optically anomalous” crystals, and Jennifer Swift, Ben Negin, Miki Kunitake and Kraig Steffen have used AFM to study, in real time and with nanometer resolution, the influence of lattice structure, solvent, and additives on the dissolution of organic crystals. The inset in Figure 2 shows the AFM image of a pit on the (001) surface of crystalline benzoin. Each terrace is one molecule high. An in situ motion picture yielded kinetic data showing that a critical a-width of 860 molecular chains was required for the pit to elongate. Such direct observation will be indispensable in transforming the venerable art of crystal growth into a science.

We believe this kind of physical-organic chemistry will make a unique contribution to the rapidly developing field of materials science.

Education

B.A. Harvard University, 1962 Ph.D. Harvard University, 1967

Honors

  • Alfred P. Sloan Fellowship, 1972
  • Camille and Henry Dreyfus Teacher-Scholar, 1972-77
  • Nobel Laureate Signature Award in Graduate Education, 1987
  • Prelog Medal, 1992
  • Catalyst Award of the Chemical Manufacturers Association, 1996

Recent Publications

Photochemical Mechanism in Single Crystals: FTIR Studies of Diacyl Peroxides. M. D. Hollingsworth and J. M. McBride, in D. Volman, G. S. Hammond, and K. Gollnick, eds., Advances in Photochemistry, 1990, 15, 279-379

B. Kahr & J. M. McBride. Optically Anomalous Crystals. Angew. Chem. Int. Ed. Engl, 1992, 31, 1-26.

J.A. Swift, R. Pal, & J.M. McBride. Using Hydrogen-Bonds and Herringbone Packing to Design Interfaces of 4,4'-Disubstituted meso-Hydrobenzoin Crystals. The Importance of Recognizing Unfavorable Packing Motifs. J. Am. Chem. Soc. 1998, 120, 96-104.

K. L. Pate & J. M. McBride. Using Crystal Optics to Demonstrate Single-Layer Localization of a Solid-State Chain Reaction. Helv. Chim. Acta, 2000, 83, 2352-2362.


Lectures:

lecture
flag Lecture 38 - Review: Synthesis of Cortisone
as author at  CHEM 125b: Freshman Organic Chemistry II,
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  lecture
flag Lecture 37 - Proving the Configuration of Glucose and Synthesizing Two Unnatural Products
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1500 views
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flag Lecture 36 - α-Reactivity and Condensation Reactions
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1536 views
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flag Lecture 35 - Acyl Insertions and α-Reactivity
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1395 views
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flag Lecture 34 - Acids and Acid Derivatives
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1412 views
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flag Lecture 33 - Green Chemistry; Acids and Acid Derivatives
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1593 views
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flag Lecture 32 - Measuring Bond Energies: Guest Lecture by Prof. G. Barney Ellison
as author at  CHEM 125b: Freshman Organic Chemistry II,
together with: Barney Ellison,
1217 views
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flag Lecture 31 - Periodate Cleavage, Retrosynthesis, and Green Chemistry
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1275 views
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flag Lecture 30 - Oxidation States and Mechanisms
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1612 views
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flag Lecture 29 - Imines and Enamines; Oxidation and Reduction
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1730 views
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flag Lecture 28 - Mechanism and Equilibrium of Carbonyl Reactions
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1447 views
  lecture
flag Lecture 27 - Triphenylmethyl and an Introduction to Carbonyl Chemistry
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1565 views
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flag Lecture 26 - Aromatic Substitution in Synthesis: Friedel-Crafts and Moses Gomberg
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1504 views
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flag Lecture 25 - C-13 and 2D NMR – Electrophilic Aromatic Substitution
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1508 views
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flag Lecture 24 - Higher-Order Effects, Dynamics, and the NMR Time Scale
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1552 views
  lecture
flag Lecture 23 - Diamagnetic Anisotropy and Spin-Spin Splitting
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1460 views
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flag Lecture 21 - Functional Groups and Fingerprints in IR Spectroscopy; Precession of Magnetic Nuclei
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1794 views
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flag Lecture 22 - Medical MRI and Chemical NMR
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1931 views
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flag Lecture 20 - Electronic and Vibrational Spectroscopy
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1570 views
  lecture
flag Lecture 19 - Aromatic Transition States: Cycloaddition and Electrocyclic Reactions
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1845 views
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flag Lecture 18 - Linear and Cyclic Conjugation Theory; 4n+2 Aromaticity
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2169 views
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flag Lecture 17 - Alkynes; Conjugation in Allylic Intermediates and Dienes
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1361 views
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flag Lecture 16 - Isoprenoids, Rubber, and Tuning Polymer Properties
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1520 views
  lecture
flag Lecture 15 - Metals and Catalysis in Alkene Oxidation, Hydrogenation, Metathesis, and Polymerization
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1996 views
lecture
flag Lecture 13 - Addition to Form Three-Membered Rings: Carbenoids and Epoxidation
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1632 views
  lecture
flag Lecture 12 - Nucleophilic Participation During Electrophilic Addition to Alkenes: Halogen, Carbene, and Borane
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1579 views
lecture
flag Lecture 11 - Carbocations and the Mechanism of Electrophilic Addition to Alkenes and Alkynes
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1585 views
  lecture
flag Lecture 9 - Pentavalent Carbon? E2, SN1, E1
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1508 views
lecture
flag Lecture 10 - Cation Intermediates – Alkenes: Formation, Addition, and Stability
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1451 views
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flag Lecture 14 - Epoxide Opening, Dipolar Cycloaddition, and Ozonolysis
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1590 views
lecture
flag Lecture 8 - Solvent, Leaving Group, Bridgehead Substitution, and Pentavalent Carbon
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1386 views
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flag Lecture 7 - Nucleophilic Substitution Tools - Stereochemistry, Rate Law, Substrate, Nucleophile, Leaving Group
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1710 views
lecture
flag Lecture 6 - Brønsted Acidity and the Generality of Nucleophilic Substitution
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1642 views
  event
flag CHEM 125b: Freshman Organic Chemistry II
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lecture
flag Lecture 5 - Solvation, H-Bonding, and Ionophores
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flag Lecture 4 - Electronegativity, Bond Strength, Electrostatics, and Non-Bonded Interactions
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1654 views
lecture
flag Lecture 3 - Rate and Selectivity in Radical-Chain Reactions
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1593 views
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flag Lecture 2 - Peculiar Rate Laws, Bond Dissociation Energies, and Relative Reactivities
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1677 views
lecture
flag Lecture 1 - Mechanism: How Energies and Kinetic Order Influence Reaction Rates
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2988 views
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flag Lecture 36 - Bond Energies, the Boltzmann Factor and Entropy
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flag Lecture 35 - Understanding Molecular Structure and Energy through Standard Bonds
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flag Lecture 34 - Sharpless Oxidation Catalysts and the Conformation of Cycloalkanes
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flag Lecture 33 - Conformational Energy and Molecular Mechanics
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flag Lecture 32 - Stereotopicity and Baeyer Strain Theory
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flag Lecture 31 - Preparing Single Enantiomers and Conformational Energy
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flag Lecture 30 - Esomeprazole as an Example of Drug Testing and Usage
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flag Lecture 29 - Preparing Single Enantiomers and the Mechanism of Optical Rotation
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2573 views
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flag Lecture 28 - Stereochemical Nomenclature; Racemization and Resolution
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flag Lecture 27 - Communicating Molecular Structure in Diagrams and Words
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flag Lecture 26 - Van't Hoff's Tetrahedral Carbon and Chirality
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flag Lecture 25 - Models in 3D Space (1869-1877); Optical Isomers
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2968 views
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flag Lecture 24 - Determining Chemical Structure by Isomer Counting (1869)
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2517 views
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flag Lecture 23 - Valence Theory and Constitutional Structure (1858)
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flag Lecture 22 - Radical and Type Theories (1832-1850)
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2607 views
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flag Lecture 21 - Berzelius to Liebig and Wöhler (1805-1832)
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flag Lecture 20 - Rise of the Atomic Theory (1790-1805)
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flag Lecture 19 - Oxygen and the Chemical Revolution (Beginning to 1789)
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flag Lecture 18 - Amide, Carboxylic Acid and Alkyl Lithium
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flag Lecture 17 - Reaction Analogies and Carbonyl Reactivity
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2757 views
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flag Lecture 16 - Recognizing Functional Groups
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2742 views
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flag Lecture 15 - Chemical Reactivity: SOMO, HOMO, and LUMO
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4034 views
  lecture
flag Lecture 14 - Checking Hybridization Theory with XH3
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2524 views
lecture
flag Lecture 13 - Overlap and Energy-Match
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2513 views
  lecture
flag Lecture 12 - Overlap and Atom-Pair Bonds
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2725 views
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flag CHEM 125 - Freshman Organic Chemistry
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11788 views
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flag Lecture 11 - Orbital Correction and Plum-Pudding Molecules
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2825 views
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flag Lecture 10 - Reality and the Orbital Approximation
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2931 views
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flag Lecture 9 - Chladni Figures and One-Electron Atoms
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3017 views
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flag Lecture 8 - One-Dimensional Wave Functions
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3390 views
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flag Lecture 7 - Quantum Mechanical Kinetic Energy
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3630 views
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flag Lecture 6 - Seeing Bonds by Electron Difference Density
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3176 views
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flag Lecture 5 - X-Ray Diffraction
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6714 views
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flag Lecture 4 - Coping with Smallness and Scanning Probe Microscopy
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2785 views
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flag Lecture 3 - Double Minima, Earnshaw's Theorem and Plum-Puddings
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3284 views
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flag Lecture 2 - Force Laws, Lewis Structures and Resonance
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5123 views
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flag Lecture 1 - How Do You Know? Freshman Organic Chemistry
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