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NO2 bond cleavage by MoL3 complexes

journal contribution
posted on 2023-05-18, 07:57 authored by Shaw, MF, Mahdizadeh Ghohe, N, Alireza AriafardAlireza Ariafard, Brookes, NJ, Stranger, R, Brian YatesBrian Yates
The cleavage of one N–O bond in NO2 by two equivalents of Mo(NRAr)3 has been shown to occur to form molybdenum oxide and nitrosyl complexes. The mechanism and electronic rearrangement of this reaction was investigated using density functional theory, using both a model Mo(NH2)3 system and the full [N(tBu)(3,5-dimethylphenyl)] experimental ligand. For the model ligand, several possible modes of coordination for the resulting complex were observed, along with isomerisation and bond breaking pathways. The lowest barrier for direct bond cleavage was found to be via the singlet η2-N,O complex (7 kJ mol−1). Formation of a bimetallic species was also possible, giving an overall decrease in energy and a lower barrier for reaction (3 kJ mol−1). Results for the full ligand showed similar trends in energies for both isomerisation between the different isomers, and for the mononuclear bond cleavage. The lowest calculated barrier for cleavage was only 21 kJ mol−1via the triplet η1-O isomer, with a strong thermodynamic driving force to the final products of the doublet metal oxide and a molecule of NO. Formation of the full ligand dinuclear complex was not accompanied by an equivalent decrease in energy seen with the model ligand. Direct bond cleavage via an η1-O complex is thus the likely mechanism for the experimental reaction that occurs at ambient temperature and pressure. Unlike the other known reactions between MoL3 complexes and small molecules, the second equivalent of the metal does not appear to be necessary, but instead irreversibly binds to the released nitric oxide.

History

Publication title

Dalton Transactions

Volume

43

Issue

4

Pagination

1620-1629

ISSN

1477-9226

Department/School

School of Natural Sciences

Publisher

Royal Soc Chemistry

Place of publication

Thomas Graham House, Science Park, Milton Rd, Cambridge, England, Cambs, Cb4 0Wf

Rights statement

Copyright 2014 The Royal Society of Chemistry

Repository Status

  • Restricted

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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