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Issue 5, 2017
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Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti<img border='0' src='http://www.rsc.org/images/entities/h2_char_e001.gif' alt='[double bond, length as m-dash]'/>NAd (Ad = adamantyl)

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Abstract

Application of the diamide, diimine {–CH[double bond, length as m-dash]N(1,2-C6H4)N(2,6-iPr2-C6H3)}2m ((dadi)m) ligand to titanium provided adducts (dadi)TiLx (1-Lx; Lx = THF, PMe2Ph, (CNMe)2), which possess the redox formulation [(dadi)4−]Ti(IV)Lx, and 22 πe (4n + 2). Related complexes containing titanium-ligand multiple bonds, (dadi)Ti[double bond, length as m-dash]X (2[double bond, length as m-dash]X; X = O, NAd), exhibit a different dadi redox state, [(dadi)2−]Ti(IV)X, consistent with 20 πe (4n). The Redox Non-Innocence (RNI) displayed by dadim impedes binding by CO, and permits catalytic conversion of AdN3 + CO to AdNCO + N2. Kinetics measurements support carbonylation of 2[double bond, length as m-dash]NAd as the rate determining step. Structural and computational evidence for the observed RNI is provided.

Graphical abstract: Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti<img border='0' src='http://www.rsc.org/images/entities/char_e001.gif' alt='[double bond, length as m-dash]'/>NAd (Ad = adamantyl)

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Publication details

The article was received on 22 Dec 2016, accepted on 03 Mar 2017 and first published on 06 Mar 2017


Article type: Edge Article
DOI: 10.1039/C6SC05610E
Citation: Chem. Sci., 2017,8, 3410-3418
  • Open access: Creative Commons BY-NC license
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    Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti<img border='0' src='http://www.rsc.org/images/entities/h2_char_e001.gif' alt='[double bond, length as m-dash]'/>NAd (Ad = adamantyl)

    S. P. Heins, P. T. Wolczanski, T. R. Cundari and S. N. MacMillan, Chem. Sci., 2017, 8, 3410
    DOI: 10.1039/C6SC05610E

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