Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti Created by potrace 1.16, written by Peter Selinger 2001-2019 NAd (Ad = adamantyl)

Redox non-innocence of the dadi ligand permits nitrene carbonylation catalysis by (dadi)Ti Ad (Ad = adamantyl). Application of the diamide, diimine {–CH N(1,2-C 6 H 4 )N(2,6- i Pr 2 -C 6 H 3 )} 2 m ((dadi) m ) ligand to titanium provided adducts (dadi)TiL x ( 1 -L x ; L x = THF, PMe 2 Ph, (CNMe) 2 )...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2017-03, Vol.8 (5), p.3410-3418
Main Authors: Heins, Spencer P., Wolczanski, Peter T., Cundari, Thomas R., MacMillan, Samantha N.
Format: Article
Language:English
Subjects:
Chemistry
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Summary:Redox non-innocence of the dadi ligand permits nitrene carbonylation catalysis by (dadi)Ti Ad (Ad = adamantyl). Application of the diamide, diimine {–CH N(1,2-C 6 H 4 )N(2,6- i Pr 2 -C 6 H 3 )} 2 m ((dadi) m ) ligand to titanium provided adducts (dadi)TiL x ( 1 -L x ; L x = THF, PMe 2 Ph, (CNMe) 2 ), which possess the redox formulation [(dadi) 4– ]Ti( iv )L x , and 22 πe – (4 n + 2). Related complexes containing titanium-ligand multiple bonds, (dadi)Ti X ( 2 X; X = O, NAd), exhibit a different dadi redox state, [(dadi) 2– ]Ti( iv )X, consistent with 20 πe – (4 n ). The Redox Non-Innocence (RNI) displayed by dadi m impedes binding by CO, and permits catalytic conversion of AdN 3 + CO to AdNCO + N 2 . Kinetics measurements support carbonylation of 2 NAd as the rate determining step. Structural and computational evidence for the observed RNI is provided.
ISSN:2041-6520
2041-6539
DOI:10.1039/c6sc05610e