 |
| Born Greenville, South Carolina, 1955. |
| University of South Carolina, B.S., 1976. |
| Indiana University, Ph.D., 1980. |
| California Institute of Technology, Postdoctoral Research Associate, 1980-83. |
| The University of Chicago, Professor, 1983-. |
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| Accolades |
| Phi Beta Kappa. |
| Sigma Xi. |
| 1997 Llewellyn John and Harriet Manchester Quantrell Award for Excellence in Undergraduate Teaching, The University of Chicago. |
| 1990-1992 Union Carbide Innovation Recognition Award. |
| 1989-1991 Alfred P. Sloan Fellow. |
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| Gregory L. Hillhouse |
| Professor |
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| Research Interests: |
| Much of my group´s research efforts revolves around the study of the transition-metal-mediated reactions of small, energy-rich molecules of fundamental significance in inorganic, bioinorganic, and organometallic chemistry. Specific projects include: |
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| I. Preparation and Study of Metal Complexes of Nitroxyl (NH=O). |
The nitrosonium cation (NO+), the nitroside anion (NO), as well as the conjugate acid of NO, nitroxyl (NH=O), are thought to be responsible for certain aspects of the rich biological chemistry of nitric oxide (NO). Moreover,
NH=O is a common intermediate in Fe-catalyzed enzymatic
process important in the nitrogen cycle, (i.e.,
reduction of nitrite to ammonia and oxidation of ammonia
and hydroxylamine). In our studies of the coordination
chemistry of NH=O we have reported the preparation
of a nitroxyl complex of Re by oxidation of ligated
hydroxylamine, and are now extending this chemistry to
other NH2OH systems.
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Other studies concern mechanistic
aspects of "protonation" reactions of NO ligands
that give rise to stepwise reduction to NH=O and ultimately
NH2OH.
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Our recent discovery that nitrosonium
triflate can effect NO+ insertion into metal-hydride bonds
provides a general preparative route to M-NH=O complexes,
a finding that should greatly facilitate our studies
of the reaction chemistry of NH=O.
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| II. Atom and Group-Transfer Reactions |
Our group has a longstanding interest in reactions mediated
by transition metals in which an oxygen atom or
nitrene (NR) fragment is transferred to an organic molecule.
Our recent work in this area has centered on lateseries
metals, particularly nickel. We have found that 3-
coordinate Ni complexes containing Ni=L multiple
bonds (L = CR2, NR, PR) exhibit unique group-transfer
reactivity, for example to olefins, and will continue to
feature these and related reactions in our future research
efforts. Illustrated below is the conversion of a Ni(I)
amide to a Ni(II)+ cation by oxidation; deprotonation
yields the first imido complex of a d8 metal (structure is
shown in the figure).
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The nitrene fragment can subsequently be transferred to
unsaturated substrates, as illustrated below in its reactions
with ethylene (to give an aziridine) and carbon monoxide
(forming an isocyanate). Similar group-transfers are
observed for the related carbene and phosphinidene
complexes (dtbpe)Ni=CPh2 and (dtbpe)Ni=PR. |
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| Selected References |
| Formation of Phosphirenes by Phosphinidene Group-Transfer Reactions from (dtbpe)Ni=P(dmp) to Alkynes. Organometallics, 22, 5182 (2003). |
| A New Route to Coordination
Complexes of Nitroxyl (HN=O)
via Insertion Reactions of
Nitrosonium Triflate with
Transition-Metal Hydrides. J. Am. Chem. Soc., 124, 12068 (2002). |
| Group Transfer from Nickel Imido,
Phosphinidene, and Carbene
Complexes to Ethylene with
Formation of Aziridine,
Phosphirane, and Cyclopropane
Products. J. Am. Chem. Soc., 125, 13350 (2003). |
| Interactions of Aziridines with
Nickel Complexes: Oxidative-
Addition and Reductive-
Elimination Reactions that Break
and Make C-N Bonds. J. Am. Chem. Soc., 124, 2890 (2002). |
| Isocyanate and Carbodiimide
Synthesis by Nitrene-Group-
Transfer from a Nickel(II) Imido
Complex. J. Chem. Soc., Chem.
Commun., 1840 (2002). |
| Monomeric Phosphido and
Phosphinidene Complexes of
Nickel. J. Am. Chem. Soc., 124, 3846 (2002). |
| Synthesis, Structure, and
Reactions of a Nitroxyl
Complex of Iridium(III), cis,
trans-IrHCl2(NH=O)(PPh3)2. J. Chem. Soc., Chem. Commun., 660 (2002). |
| Synthesis, Structure, and Reactions
of a Three-Coordinate Nickel-
Carbene Complex, {1,2-bis(di-tertbutylphosphino)
ethane}Ni=CPh2. J. Am. Chem. Soc., 124, 9976 (2002). |
| Terminal Amido and Imido Complexes of Three-Coordinate Nickel. J. Am. Chem. Soc., 123, 4623 (2001). |
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Inorganic Chemistry 