Issue 5, 2017

Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti[double bond, length as m-dash]NAd (Ad = adamantyl)

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 [[double bond, length as m-dash]] NAd (Ad = adamantyl)

Supplementary files

Article information

Article type
Edge Article
Submitted
22 Dec 2016
Accepted
03 Mar 2017
First published
06 Mar 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2017,8, 3410-3418

Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti[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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