Jump to main content
US EPA
United States Environmental Protection Agency
Search
Search
Main menu
Environmental Topics
Laws & Regulations
About EPA
Health & Environmental Research Online (HERO)
Contact Us
Print
Feedback
Export to File
Search:
This record has one attached file:
Add More Files
Attach File(s):
Display Name for File*:
Save
Citation
Tags
HERO ID
1000995
Reference Type
Journal Article
Title
Protonation of the Dinitrogen-Reduction Catalyst [HIPTN(3)N]Mo(III) Investigated by ENDOR Spectroscopy
Author(s)
Kinney, RA; McNaughton, RL; Chin, JM; Schrock, RR; Hoffman, BM
Year
2011
Is Peer Reviewed?
Yes
Journal
Inorganic Chemistry
ISSN:
0020-1669
EISSN:
1520-510X
Volume
50
Issue
2
Page Numbers
418-420
Language
English
PMID
21155580
DOI
10.1021/ic102127v
Abstract
Dinitrogen is reduced to ammonia by the molybdenum complex of L = [HIPTN(3)N](3-) [Mo; HIPT = 3,5-(2,4,6-iPr(3)C(6)H(2))(2)C(6)H(3)]. The mechanism by which this occurs involves the stepwise addition of proton/electron pairs, but how the first pair converts MoN(2) to MoN═NH remains uncertain. The first proton of reduction might bind either at N(β) of N(2) or at one of the three amido nitrogen (N(am)) ligands. Treatment of MoCO with [2,4,6-Me(3)C(5)H(3)N]BAr'(4) [Ar' = 2,3-(CF(3))(2)C(6)H(3)] in the absence of reductant generates HMoCO(+), whose electron paramagnetic resonance spectrum has greatly reduced g anisotropy relative to MoCO. (2)H Mims pulsed electron nuclear double-resonance spectroscopy of (2)HMoCO(+) shows a signal that simulations show to have a hyperfine tensor with an isotropic coupling, a(iso)((2)H) = -0.22 MHz, and a roughly dipolar anisotropic interaction, T((2)H) = [-0.48, -0.93, 1.42] MHz. The simulations show that the deuteron is bound to N(am), near the Mo equatorial plane, not along the normal, and at a distance of 2.6 Å from Mo, which is nearly identical with the (N(am))(2)H(+)-Mo distance predicted by density functional theory computations.
Tags
IRIS
•
Ammonia
Literature Search – March 2012 (private)
Literature Search Results
Home
Learn about HERO
Using HERO
Search HERO
Projects in HERO
Risk Assessment
Transparency & Integrity