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Title: Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti=NAd (Ad = adamantyl)

Application of the diamide, diimine {–CH=N(1,2-C 6H 4)N(2,6- iPr 2-C 6H 3)} 2 m ((dadi) m) ligand to titanium provided adducts (dadi)TiL x (1-L x; L x = THF, PMe 2Ph, (CNMe) 2), which possess the redox formulation [(dadi) 4-]Ti(IV)L x, and 22 πe - (4n + 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 - (4n). 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. Finally, structural and computational evidence for the observed RNI is provided.
Authors:
 [1] ; ORCiD logo [1] ;  [2] ;  [1]
  1. Cornell Univ., Ithaca, NY (United States). Baker Lab. and Dept. of Chemistry and Chemical Biology
  2. Univ. of North Texas, Denton, TX (United States). The Center for Advanced Scientific Computing and Modeling and Dept. of Chemistry
Publication Date:
Grant/Contract Number:
FG02-03ER15387; CHE-1402149; CHE-1531468; CHE-1531632
Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 5; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Research Org:
Univ. of North Texas, Denton, TX (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); Cornell Univ., Ithaca, NY (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
OSTI Identifier:
1429375

Heins, Spencer P., Wolczanski, Peter T., Cundari, Thomas R., and MacMillan, Samantha N.. Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti=NAd (Ad = adamantyl). United States: N. p., Web. doi:10.1039/c6sc05610e.
Heins, Spencer P., Wolczanski, Peter T., Cundari, Thomas R., & MacMillan, Samantha N.. Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti=NAd (Ad = adamantyl). United States. doi:10.1039/c6sc05610e.
Heins, Spencer P., Wolczanski, Peter T., Cundari, Thomas R., and MacMillan, Samantha N.. 2017. "Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti=NAd (Ad = adamantyl)". United States. doi:10.1039/c6sc05610e. https://www.osti.gov/servlets/purl/1429375.
@article{osti_1429375,
title = {Redox non-innocence permits catalytic nitrene carbonylation by (dadi)Ti=NAd (Ad = adamantyl)},
author = {Heins, Spencer P. and Wolczanski, Peter T. and Cundari, Thomas R. and MacMillan, Samantha N.},
abstractNote = {Application of the diamide, diimine {–CH=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=X (2=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=NAd as the rate determining step. Finally, structural and computational evidence for the observed RNI is provided.},
doi = {10.1039/c6sc05610e},
journal = {Chemical Science},
number = 5,
volume = 8,
place = {United States},
year = {2017},
month = {3}
}