Heterobimetallic Ti/Co Complexes That Promote Catalytic N–N Bond Cleavage

Treatment of the tris­(phosphinoamide) titanium precursor ClTi­(XylNP i Pr2)3 (1) with CoI2 leads to the heterobimetallic complex (η2- i Pr2PNXyl)­Ti­(XylNP i Pr2)2(μ-Cl)­CoI (2). One-electron reduction of 2 affords (η2- i Pr2PNXyl)­Ti­(XylNP i Pr2)2CoI (3), which can be reduced by another electron...

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Bibliographic Details
Published in:Inorganic chemistry 2015-11, Vol.54 (22), p.10909-10917
Main Authors: Wu, Bing, Gramigna, Kathryn M, Bezpalko, Mark W, Foxman, Bruce M, Thomas, Christine M
Format: Article
Language:English
Subjects:
Bonding
Cleavage
Diamagnetism
Hydrazines
Ligands
Nitrogen compounds
Precursors
Titanium
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Summary:Treatment of the tris­(phosphinoamide) titanium precursor ClTi­(XylNP i Pr2)3 (1) with CoI2 leads to the heterobimetallic complex (η2- i Pr2PNXyl)­Ti­(XylNP i Pr2)2(μ-Cl)­CoI (2). One-electron reduction of 2 affords (η2- i Pr2PNXyl)­Ti­(XylNP i Pr2)2CoI (3), which can be reduced by another electron under dinitrogen to generate the reduced diamagnetic complex (THF)­Ti­(XylNP i Pr2)3CoN2 (4). The removal of the dinitrogen ligand from 4 under vacuum affords (THF)­Ti­(XylNP i Pr2)3Co (5), which features a Ti–Co triple bond. Treatment of 4 with hydrazine or methyl hydrazine results in N–N bond cleavage and affords the new diamagnetic complexes (L)­Ti­(XylNP i Pr2)3CoN2 (L = NH3 (6), MeNH2 (7)). Complexes 4, 5, and 6 have been shown to catalyze the disproportionation of hydrazine into ammonia and dinitrogen gas through a mechanism involving a diazene intermediate.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.5b01962