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

Bing Wu; Kathryn M Gramigna; Mark W Bezpalko; Bruce M Foxman; Christine M Thomas

doi:10.1021/acs.inorgchem.5b01962

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

Journal article

Peer reviewed

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

Bing Wu, Kathryn M Gramigna, Mark W Bezpalko, Bruce M Foxman and Christine M Thomas

Inorganic chemistry, Vol.54(22), pp.10909-10917

11/16/2015

DOI: https://doi.org/10.1021/acs.inorgchem.5b01962

PMID: 26492046

Abstract

Redox reactions

Ammonia

Molecules

Nitrogen

Ligands

Treatment of the tris(phosphinoamide) titanium precursor ClTi(XylNP(i)Pr2)3 (1) with CoI2 leads to the heterobimetallic complex (η(2)-(i)Pr2PNXyl)Ti(XylNP(i)Pr2)2(μ-Cl)CoI (2). One-electron reduction of 2 affords (η(2)-(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.

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Title: Heterobimetallic Ti/Co Complexes That Promote Catalytic N-N Bond Cleavage
Creators: Bing Wu - Department of Chemistry, Brandeis University , 415 South Street, Waltham, Massachusetts 02454, United States
Kathryn M Gramigna - Department of Chemistry, Brandeis University , 415 South Street, Waltham, Massachusetts 02454, United States
Mark W Bezpalko - Department of Chemistry, Brandeis University , 415 South Street, Waltham, Massachusetts 02454, United States
Bruce M Foxman - Department of Chemistry, Brandeis University , 415 South Street, Waltham, Massachusetts 02454, United States
Christine M Thomas - Department of Chemistry, Brandeis University , 415 South Street, Waltham, Massachusetts 02454, United States
Publication Details: Inorganic chemistry, Vol.54(22), pp.10909-10917
Identifiers: 9923989473201921
Academic Unit: Department of Chemistry
Language: English
Resource Type: Journal article

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

Abstract

UN Sustainable Development Goals (SDGs)

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