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Mechanistic Insight into the Reactivity of Oxotransferases by Novel Asymmetric Dioxomolybdenum(VI) Model Complexes
Author(s) -
Mayilmurugan Ramasamy,
Harum Bastian N.,
Volpe Manuel,
Sax Alexander F.,
Palaniandavar Mallayan,
MöschZanetti Nadia C.
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201001177
Subject(s) - chemistry , molybdenum , reactivity (psychology) , octahedron , redox , crystallography , electrochemistry , catalysis , stereochemistry , crystal structure , inorganic chemistry , organic chemistry , medicine , alternative medicine , electrode , pathology
The asymmetric molybdenum(VI) dioxo complexes of the bis(phenolate) ligands 1,4‐bis(2‐hydroxybenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐4‐methylbenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐3,5‐dimethylbenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐3,5‐di‐ tert ‐butylbenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐4‐flurobenzyl)‐1,4‐diazepane, and 1,4‐bis(2‐hydroxy‐4‐chlorobenzyl)‐1,4‐diazepane (H 2 (L1)–H 2 (L6), respectively) have been isolated and studied as functional models for molybdenum oxotransferase enzymes. These complexes have been characterized as asymmetric complexes of type [MoO 2 (L)] 1–6 by using NMR spectroscopy, mass spectrometry, elemental analysis, and electrochemical methods. The molecular structures of [MoO 2 (L)] 1–4 have been successfully determined by single‐crystal X‐ray diffraction analyses, which show them to exhibit a distorted octahedral coordination geometry around molybdenum(VI) in an asymmetrical cis ‐β configuration. The MoO oxo bond lengths differ only by ≈0.01 Å. Complexes 1 , 2 , 5 , and 6 exhibit two successive Mo VI /Mo V ( E 1/2, −1.141 to −1.848 V) and Mo V /Mo IV ( E 1/2, −1.531 to −2.114 V) redox processes. However, only the Mo VI /Mo V redox couple was observed for 3 and 4 , suggesting that the subsequent reduction of the molybdenum(V) species is difficult. Complexes 1 , 2 , 5 , and 6 elicit efficient catalytic oxygen‐atom transfer (OAT) from dimethylsulfoxide (DMSO) to PMe 3 at 65 °C at a significantly faster rate than the symmetric molybdenum(VI) complexes of the analogous linear bis(phenolate) ligands known so far to exhibit OAT reactions at a higher temperature (130 °C). However, complexes 3 and 4 fail to perform the OAT reaction from DMSO to PMe 3 at 65 °C. DFT/B3LYP calculations on the OAT mechanism reveal a strong trans effect.