Abstract

The long-term objectives of this research are to determine how molecular nitrogen can be reduced to ammonia under ambient conditions employing a well-defined transition metal complex, protons, and electrons, and/or to some organic molecule that contains nitrogen, at first stoichiometrically, and ultimately catalytically. The near-term objective is to prepare new di- or triamido/donor ligands and explore the chemistry of (primarily) Mo complexes that contain these ligands, especially chemistry that is relevant to the reduction of dinitrogen, including the chemistry of complexes that contain N2RX (X=0-4) or NRy (y=0-3) ligands. In general we wish to determine what principles are of fundamental and general significance to the activation and reduction of dinitrogen at one or two metal centers (homobimetallic or heterobimetallic). We will focus molybdenum as the activating metal for dinitrogen, although analogous chemistry of tungsten will be carried out in order to compare it to molybdenum. The most common metal to be employed in heterobimetallic chemistry will be iron.

  Funding Agency

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
5R01GM031978-19
Application #
6476438
Study Section
Metallobiochemistry Study Section (BMT)
Program Officer
Preusch, Peter C
Project Start
1983-04-01
Project End
2002-11-30
Budget Start
2001-12-01
Budget End
2002-11-30
Support Year
19
Fiscal Year
2002
Total Cost
$202,359
Indirect Cost

  Institution

Name
Massachusetts Institute of Technology
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
City
Cambridge
State
MA
Country
United States
Zip Code
02139

  Publications

Sharma, Ajay; Roemelt, Michael; Reithofer, Michael et al. (2017) EPR/ENDOR and Theoretical Study of the Jahn-Teller-Active [HIPTN3N]MoVL Complexes (L = N-, NH). Inorg Chem 56:6906-6919
Kinney, R Adam; McNaughton, Rebecca L; Chin, Jia Min et al. (2011) Protonation of the dinitrogen-reduction catalyst [HIPTN3N]Mo(III) investigated by ENDOR spectroscopy. Inorg Chem 50:418-20
Kinney, R Adam; Hetterscheid, Dennis G H; Hanna, Brian S et al. (2010) Formation of {[HIPTN(3)N]Mo(III)H}(-) by heterolytic cleavage of H(2) as established by EPR and ENDOR spectroscopy. Inorg Chem 49:704-13
McNaughton, Rebecca L; Roemelt, Michael; Chin, Jia Min et al. (2010) Experimental and theoretical EPR study of Jahn-Teller-active [HIPTN(3)N]MoL complexes (L = N(2), CO, NH(3)). J Am Chem Soc 132:8645-56
Chin, J M; Schrock, R R; Müller, P (2010) Synthesis of diamidopyrrolyl molybdenum complexes relevant to reduction of dinitrogen to ammonia. Inorg Chem 49:7904-16
Reithofer, Michael R; Schrock, Richard R; Müller, Peter (2010) Synthesis of [(DPPNCH2CH2)3N]3- molybdenum complexes (DPP = 3,5-(2,5-Diisopropylpyrrolyl)2C6H3) and studies relevant to catalytic reduction of dinitrogen. J Am Chem Soc 132:8349-58
Hetterscheid, Dennis G H; Hanna, Brian S; Schrock, Richard R (2009) Molybdenum triamidoamine systems. Reactions involving dihydrogen relevant to catalytic reduction of dinitrogen. Inorg Chem 48:8569-77
Kupfer, Thomas; Schrock, Richard R (2009) Alkylation of dinitrogen in [(HIPTNCH(2)CH(2))(3)N]Mo complexes (HIPT = 3,5-(2,4,6-i-Pr(3)C(6)H(2))(2)C(6)H(3)). J Am Chem Soc 131:12829-37
Schrock, Richard R (2008) Catalytic reduction of dinitrogen to ammonia by molybdenum: theory versus experiment. Angew Chem Int Ed Engl 47:5512-22
McNaughton, Rebecca L; Chin, Jia Min; Weare, Walter W et al. (2007) EPR study of the low-spin [d(3);S =(1)/(2)], Jahn-Teller-active, dinitrogen complex of a molybdenum trisamidoamine. J Am Chem Soc 129:3480-1

Showing the most recent 10 out of 23 publications