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

Abstract

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.

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:
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)
OSTI Identifier:
1429375
Grant/Contract Number:  
FG02-03ER15387; CHE-1402149; CHE-1531468; CHE-1531632
Resource 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
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

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., 2017. 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. Mon . "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}
}

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    Works referencing / citing this record:

    Four-Electron Oxidative Formation of Aryl Diazenes Using a Tantalum Redox-Active Ligand Complex
    journal, June 2008

    • Zarkesh, Ryan A.; Ziller, Joseph W.; Heyduk, Alan F.
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    Nitrene Insertion into CC and CH Bonds of Diamide Diimine Ligands Ligated to Chromium and Iron
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    • Heins, Spencer P.; Morris, Wesley D.; Wolczanski, Peter T.
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    • DOI: 10.1002/anie.201507463

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    • Fout, Alison R.; Kilgore, Uriah J.; Mindiola, Daniel J.
    • Chemistry - A European Journal, Vol. 13, Issue 34
    • DOI: 10.1002/chem.200701064

    N–H Group Transfer and Oxidative Addition Chemistry Promoted by Isolable Bis(cyclopentadienyl)titanium Sandwich Complexes
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    • Hanna, Tamara E.; Lobkovsky, Emil; Chirik, Paul J.
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    • DOI: 10.1002/ejic.200601134

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    Reactions and Applications of Titanium Imido Complexes
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    • Hazari, Nilay; Mountford, Philip
    • Accounts of Chemical Research, Vol. 38, Issue 11
    • DOI: 10.1021/ar030244z

    Redox Non-Innocent Ligands: Versatile New Tools to Control Catalytic Reactions
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    • Lyaskovskyy, Volodymyr; de Bruin, Bas
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    Tris(3,5-di- tert -butylcatecholato)molybdenum(VI): Lewis Acidity and Nonclassical Oxygen Atom Transfer Reactions
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    • DOI: 10.1021/ic401736f

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    • DOI: 10.1021/ic5001123

    Iron and Chromium Complexes Containing Tridentate Chelates Based on Nacnac and Imino- and Methyl-Pyridine Components: Triggering C—X Bond Formation
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    • Morris, Wesley D.; Wolczanski, Peter T.; Sutter, Jörg
    • Inorganic Chemistry, Vol. 53, Issue 14
    • DOI: 10.1021/ic500807y

    Metal and Ligand Effects on Bonding in Group 6 Complexes of Redox-Active Amidodiphenoxides
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    • Ranis, Leila G.; Werellapatha, Kalpani; Pietrini, Nicholas J.
    • Inorganic Chemistry, Vol. 53, Issue 19
    • DOI: 10.1021/ic501222n

    Reactions of Tetrabromocatecholatomanganese(III) Complexes with Dioxygen
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    Alkoxido, Amido, and Imido Derivatives of Titanium(IV) Tetratolylporphyrin
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    • Inorganic Chemistry, Vol. 36, Issue 3
    • DOI: 10.1021/ic960977y

    Preparation of monomeric (Me5C5)2VO and (Me5C5)2Ti(O)(L) and their decomposition to (Me5C5)4M4(.mu.-O)6
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    • Journal of the American Chemical Society, Vol. 115, Issue 15
    • DOI: 10.1021/ja00068a103

    Cleavage of the Nitrous Oxide NN Bond by a Tris(amido)molybdenum(III) Complex
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    • Laplaza, Catalina E.; Odom, Aaron L.; Davis, William M.
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    • DOI: 10.1021/ja00122a033

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    journal, May 1995

    • Groves, John T.; Roman, J. Scott
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