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Issue 43, 2018
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Molybdenum(VI) tris(amidophenoxide) complexes

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Abstract

Tris(2-(arylamido)-4,6-di-tert-butylphenoxo)molybdenum(VI) complexes (Rap)3Mo can be prepared either from (cycloheptatriene)Mo(CO)3 and the N-aryliminoquinone, or from MoO2(acac)2 and the aminophenol. In contrast to all other reported unconstrained transition metal tris(amidophenoxide) complexes, the molybdenum complexes show a facial geometry in the solid state. In solution, the fac isomer predominates, though a small amount of mer isomer is detectable at room temperature. At elevated temperature the two species interconvert through Rây-Dutt trigonal twists, which are faster than Bailar twists in this system, presumably because of steric effects of the N-aryl groups. Substituents on the N-aryl ring shift the fac/mer equilibrium of the complex, with more electron-withdrawing substituents generally increasing the proportion of the mer isomer. The preference for fac over mer geometry is thus suggested to be due to enhanced π bonding in the fac isomer. In contrast to analogous catecholate complexes, the tris(amidophenoxide) complexes are not Lewis acidic and are inert to nucleophilic oxidants such as amine-N-oxides.

Graphical abstract: Molybdenum(vi) tris(amidophenoxide) complexes

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Publication details

The article was received on 19 Aug 2018, accepted on 15 Oct 2018 and first published on 16 Oct 2018


Article type: Paper
DOI: 10.1039/C8DT03392G
Citation: Dalton Trans., 2018,47, 15583-15595
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    Molybdenum(VI) tris(amidophenoxide) complexes

    A. N. Erickson and S. N. Brown, Dalton Trans., 2018, 47, 15583
    DOI: 10.1039/C8DT03392G

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