Faculty

Michelle MillarMichelle Millar, Associate Professor

B. S. University of California, Los Angeles, 1968
Ph.D. Massachusetts Institute of Technology, 1975
Postdoctoral Research Associate, Texas A & M University, 1975-77
Postdoctoral Research Associate, Cornell University, 1978

 

Phone: (631) 632-7909

Email:

 

 

Inorganic Chemistry

Current research is directed toward the design, synthesis, and study of new transition metal complexes that are apt to exhibit interesting structural, reactivity, and/or physical properties. Using this approach, researchers in my laboratory have made and continue to make significant discoveries related to understanding the behavior of metal centers in proteins and in industrially important catalysts.

We have pioneered the use of sterically encumbered thiolate ligands to acquire complexes that possess some of the more unusual features of metal-cysteine centers in metalloproteins. The rationale for this approach came from the thought that proteins function as sterically encumbered ligands. Correspondingly, we have isolated and characterized analogs for iron-sulfur centers in the oxidized form of rubredoxin, [Fe(SR)4]M1-, and the oxidized form of high potential iron-sulfur proteins, [Fe4S4(SR)4]1-. Work on these and other systems is being explored.

In a related area, graduate students in my group have successfully synthesized significant molecules that mimic the structural and redox characteristics of the nickel-containing hydrogenase enzymes. Some examples include the characterization of molecules with stable Ni(III)- and Ni(IV)-thiolate centers as well as Ni(II) compounds that form unusual [Ni ...HS] centers. A major objective of this research is to understand the way in which these enzymes catalyze the interconversion of H2 = 2 H + + 2 e.

Hydrogen bonding interactions of protein amide NH groups with metal-cysteine centers is an important feature of several enzymes. Our recent work has shown that similar [NH ...S-M] hydrogen bonding interactions occur in our model compounds. Using this strategy, we have designed and created elaborate chelating ligands that form a protective pocket around the catalytic metal center.

This research provides splendid opportunities for acquiring substantial skills and discoveries in several fundamental areas of chemistry.

Publications

New chemistry of sterically encumbered phosphites and phosphines. Dignam C, Jiang JF, Millar M. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 221: 221-INOR Part 1 APR 1 2001

New types of nickel compounds as analogs for the metal-sulfur centers in hydrogenase. Millar M. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 221: 574-INOR Part 1 APR 1 2001

A venture into the chemistry of hydrogen-bonding interactions in the primary and secondary coordination environment of metal-sulfur complexes: Models for the active site of hydrogenase enzymes. Millar M, Nguyen D, Voorhies H, Beatty S, Haff J, Dejean F. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 216: 351-INOR Part 2 AUG 23 1998

Ruthenium-sulfur compound: The chemistry of [Ru(CO)(3)(SR)(3)](1-) and related complexes. Haff J, Millar M. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 216: 426-INOR Part 2 AUG 23 1998

The design and synthesis of polydentate metal-thiolate complexes with functional substituents in the secondary coordination sphere. Millar M, Nguyen DH. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 213: 377-INOR Part 2 APR 13 1997

Metal thiolate monomers as models for the active site of hydrogenase. Voorhies RH, Millar M, Beatty ST.
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY,. 213: 380-INOR Part 2 APR 13 1997

Nickel(II) thiolate complex with carbon monoxide and its Fe(II) analog: Synthetic models for CO adducts of nickel-iron-containing enzymes Nguyen DH, Hsu HF, Millar M, Koch SA, Achim C, Bominaar EL, Munck E JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 118 (37): 8963-8964 SEP 18 1996

Models for the iron-sulfur protein rubredoxin: The use of sterically hindered thiolate ligands to stabilize [Fe(SR)(4)](1-) complexes: Some considerations of the structure of the [Fe(S-Cys)(4)] centers in oxidized rubredoxins Millar M, Lee JF, OSullivan T, Koch SA, Fikar R. INORGANICA CHIMICA ACTA, 243 (1-2): 333-343 FEB 29 1996

Mixed metal polythiolate complexes as models for the nickel-iron center in hydrogenase enzymes. Ai KS, Franolic J, Millar M. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 211: 587-INOR Part 1 MAR 24 1996

Monomeric Ni(III)-thiolate complexes, as model for the nickel center in [Ni-Fe] hydrogenases. Nguyen DH, Millar M. ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 211: 588-INOR Part 1 MAR 24 1996

Synthesis, structure, and properties of a binuclear iron-thiolate complex with a trans-disulfur bridge - a structural isomer of the [fe2s2] core of 2-fe ferredoxins. Franolic JD, Millar M, Koch SA. INORGANIC CHEMISTRY, 34 (8): 1981-1982 APR 12 1995

Synthesis and structure of titanium tetrathiolate and tantalum pentathiolate complexes - metal sulfur bonding in early transition-metal compounds. Corwin DT, Corning JF, Koch SA, Millar M. INORGANICA CHIMICA ACTA, 229 (1-2): 335-342 FEB 1995

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