» Articles » PMID: 30628782

Requirements for Lewis Acid-Mediated Capture and N-N Bond Cleavage of Hydrazine at Iron

Overview
Journal Inorg Chem
Specialty Chemistry
Date 2019 Jan 11
PMID 30628782
Citations 8
Authors
Affiliations
Soon will be listed here.
Abstract

An iron complex bearing a pyridine(dicarbene) pincer was designed to probe the requirements of Lewis acid-enabled NH capture and subsequent N-N bond cleavage. Appended boron Lewis acids were installed by two methods to circumvent the incompatibilities associated with Lewis acid/base quenching of free carbenes and boranes. NH capture by borane Lewis acids is dependent on both the Lewis acidity and the steric profile about boron. A substitutionally inert primary coordination sphere at iron prevents an Fe-NH interaction as well as N-N bond homolysis upon reduction.

Citing Articles

Appended Lewis Acids Enable Dioxygen Reactivity and Catalytic Oxidations with Ni(II).

Beagan D, Rivera C, Szymczak N J Am Chem Soc. 2024; 146(18):12375-12385.

PMID: 38661576 PMC: 11148854. DOI: 10.1021/jacs.3c12399.


A Bidentate Ligand Featuring Ditopic Lewis Acids in the Second Sphere for Selective Substrate Capture and Activation.

Beagan D, Kiernicki J, Zeller M, Szymczak N Angew Chem Int Ed Engl. 2023; 62(13):e202218907.

PMID: 36720708 PMC: 10023486. DOI: 10.1002/anie.202218907.


A Borane Lewis Acid in the Secondary Coordination Sphere of a Ni(II) Imido Imparts Distinct C-H Activation Selectivity.

Wang B, Seo C, Zhang C, Chu J, Szymczak N J Am Chem Soc. 2022; 144(34):15793-15802.

PMID: 35973127 PMC: 10276360. DOI: 10.1021/jacs.2c06662.


Distinct Reactivity Modes of a Copper Hydride Enabled by an Intramolecular Lewis Acid.

Norwine E, Kiernicki J, Zeller M, Szymczak N J Am Chem Soc. 2022; 144(33):15038-15046.

PMID: 35960993 PMC: 10291504. DOI: 10.1021/jacs.2c02937.


Mobility of Lewis acids within the secondary coordination sphere: toward a model for cooperative substrate binding.

Kiernicki J, Norwine E, Lovasz M, Zeller M, Szymczak N Chem Commun (Camb). 2020; 56(86):13105-13108.

PMID: 33016291 PMC: 7606458. DOI: 10.1039/d0cc05121g.


References
1.
Tondreau A, Milsmann C, Lobkovsky E, Chirik P . Oxidation and reduction of bis(imino)pyridine iron dicarbonyl complexes. Inorg Chem. 2011; 50(20):9888-95. DOI: 10.1021/ic200730k. View

2.
MacBeth C, Golombek A, Young Jr V, Yang C, Kuczera K, Hendrich M . O2 activation by nonheme iron complexes: A monomeric Fe(III)-Oxo complex derived from O2. Science. 2000; 289(5481):938-41. DOI: 10.1126/science.289.5481.938. View

3.
Hoffman B, Dean D, Seefeldt L . Climbing nitrogenase: toward a mechanism of enzymatic nitrogen fixation. Acc Chem Res. 2009; 42(5):609-19. PMC: 2684573. DOI: 10.1021/ar8002128. View

4.
Wickramasinghe L, Ogawa T, Schrock R, Muller P . Reduction of Dinitrogen to Ammonia Catalyzed by Molybdenum Diamido Complexes. J Am Chem Soc. 2017; 139(27):9132-9135. DOI: 10.1021/jacs.7b04800. View

5.
Steiner T . The hydrogen bond in the solid state. Angew Chem Int Ed Engl. 2002; 41(1):49-76. DOI: 10.1002/1521-3773(20020104)41:1<48::aid-anie48>3.0.co;2-u. View