 |
| 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: |
| |
| 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 enzymaticprocess important in the nitrogen cycle,
(i.e.,reduction of nitrite to ammonia and oxidation of ammoniaand
hydroxylamine). In our studies of the coordinationchemistry of NH=O we
have reported the preparationof a nitroxyl complex of Re by oxidation
of ligatedhydroxylamine, and are now extending this chemistry toother NH2OH
systems.
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Other
studies concern mechanisticaspects of "protonation" reactions of NO
ligandsthat give rise to stepwise reduction to NH=O and ultimatelyNH2OH.
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Our
recent discovery that nitrosoniumtriflate can effect NO+ insertion into
metal-hydride bondsprovides a general preparative route to M-NH=O
complexes,a finding that should greatly facilitate our studiesof the
reaction chemistry of NH=O.
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| II.
Atom and Group-Transfer Reactions |
Our group
has a longstanding interest in reactions mediatedby transition metals
in which an oxygen atom ornitrene (NR) fragment is transferred to an
organic molecule.Our recent work in this area has centered on
lateseriesmetals, particularly nickel. We have found that 3-coordinate
Ni complexes containing Ni=L multiplebonds (L = CR2,
NR, PR) exhibit unique group-transferreactivity, for example to
olefins, and will continue tofeature these and related reactions in our
future researchefforts. Illustrated below is the conversion of a
Ni(I)amide to a Ni(II)+ cation by oxidation; deprotonationyields the
first imido complex of a d8 metal (structure
isshown in the figure).
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The
nitrene fragment can subsequently be transferred tounsaturated
substrates, as illustrated below in its reactionswith ethylene (to give
an aziridine) and carbon monoxide(forming an isocyanate). Similar
group-transfers areobserved for the related carbene and
phosphinidenecomplexes (dtbpe)Ni=CPh2 and
(dtbpe)Ni=PR.
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| Selected
References |
| Interactions of
aziridines with nickel complexes: Oxidative-addition and
reductive-elimination reactions that break and make C–N bonds. B.
L. Lin, C. R. Clough, and G. L. Hillhouse, J. Am. Chem. Soc., 124, 2890 (2002).
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| Synthesis,
structure, and reactions of a nitroxyl complex of iridium(III),
cis,trans-IrHCl2(NH=O)(PPh3)2. R. Melenkivitz and G. L. Hillhouse, J. Chem. Soc., Chem. Commun., 660 (2002). |
| A new route to
coordination complexes of nitroxyl (HN=O) via insertion reactions of
nitrosonium triflate with transition-metal hydrides. R. Melenkivitz, J.
S. Southern, G. L. Hillhouse, T. E. Concolino, L. M. Liable-Sands, and
A. L. Rheingold, 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. R.
Waterman and G. L. Hillhouse, J. Am. Chem. Soc., 125, 13350 (2003). |
| Preparation of
stable alkyl complexes of Ni(I) and their one-electron oxidation to
nickel(II) complex cations. K. D. Kitiachvili, D. J. Mindiola, and G.
L. Hillhouse, J. Am. Chem. Soc., 126, 10554 (2004). |
| Snapshots of the oxidative-addition process of silanes to nickel(0). V. M. Iluc and G. L. Hillhouse, Tetrahedron, 62, 7577 (2006). |
| η2-Organoazide
complexes of nickel and their conversion to terminal imido complexes
via dinitrogen extrusion. R. Waterman and G. L. Hillhouse, J. Am. Chem. Soc., 130, 12628 (2008). |
| Two-coordinate d9 complexes. Synthesis and oxidation of NHC nickel(I) amides. C. A. Laskowski and G. L. Hillhouse, J. Am. Chem. Soc., 130, 13846 (2008). |
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Inorganic Chemistry 