Activation of atmospheric nitrogen and azobenzene N=N bond cleavage by a transient Nb(III) complex

Uriah J. Kilgore; Xiaofan Yang; John Tomaszewski; John C. Huffman; Daniel J. Mindiola

doi:10.1021/ic061642b

Activation of atmospheric nitrogen and azobenzene N=N bond cleavage by a transient Nb(III) complex

Uriah J. Kilgore
, Xiaofan Yang
, John Tomaszewski
, John C. Huffman
, Daniel J. Mindiola

Department of Pathology and Anatomical Sciences

Indiana University Bloomington

Research output: Contribution to journal › Article › peer-review

65 Scopus citations

Abstract

Atmospheric N₂ is activated by two transient Nb(III) "(PNP)NbCl₂" (PNP^- = N[2-P(CHMe ₂)₂-4-methylphenyl]₂) fragments to form the bridging diimido [(PNP)NbCl₂]₂(μ-N₂) (1). Complex 1 can also be independently synthesized from Nb(IV) and Nb(V) precursors via one-electron and transmetalation reactions, respectively. In the presence of azobenzene, the transient Nb(III) intermediate, prepared from Li(PNP) and NbCl₃(DME) (DME = dimethoxyethane) under Ar, cleaves the N=N bond via a metal-ligand cooperative four-electron reduction to form niobium imide and phosphoranimine functionalities. Structural studies are presented and discussed for various Nb systems bearing the pincer-type framework PNP as well as the N₂ and azobenzene activated products. Theoretical studies addressing the Nb-N₂-Nb core in 1 are also presented.

Original language	English
Pages (from-to)	10712-10721
Number of pages	10
Journal	Inorganic Chemistry
Volume	45
Issue number	26
DOIs	https://doi.org/10.1021/ic061642b
State	Published - Dec 25 2006

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title = "Activation of atmospheric nitrogen and azobenzene N=N bond cleavage by a transient Nb(III) complex",

abstract = "Atmospheric N2 is activated by two transient Nb(III) {"}(PNP)NbCl2{"} (PNP- = N[2-P(CHMe 2)2-4-methylphenyl]2) fragments to form the bridging diimido [(PNP)NbCl2]2(μ-N2) (1). Complex 1 can also be independently synthesized from Nb(IV) and Nb(V) precursors via one-electron and transmetalation reactions, respectively. In the presence of azobenzene, the transient Nb(III) intermediate, prepared from Li(PNP) and NbCl3(DME) (DME = dimethoxyethane) under Ar, cleaves the N=N bond via a metal-ligand cooperative four-electron reduction to form niobium imide and phosphoranimine functionalities. Structural studies are presented and discussed for various Nb systems bearing the pincer-type framework PNP as well as the N2 and azobenzene activated products. Theoretical studies addressing the Nb-N2-Nb core in 1 are also presented.",

author = "Kilgore, \{Uriah J.\} and Xiaofan Yang and John Tomaszewski and Huffman, \{John C.\} and Mindiola, \{Daniel J.\}",

year = "2006",

month = dec,

day = "25",

doi = "10.1021/ic061642b",

language = "English",

volume = "45",

pages = "10712--10721",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Activation of atmospheric nitrogen and azobenzene N=N bond cleavage by a transient Nb(III) complex

AU - Kilgore, Uriah J.

AU - Yang, Xiaofan

AU - Tomaszewski, John

AU - Huffman, John C.

AU - Mindiola, Daniel J.

PY - 2006/12/25

Y1 - 2006/12/25

N2 - Atmospheric N2 is activated by two transient Nb(III) "(PNP)NbCl2" (PNP- = N[2-P(CHMe 2)2-4-methylphenyl]2) fragments to form the bridging diimido [(PNP)NbCl2]2(μ-N2) (1). Complex 1 can also be independently synthesized from Nb(IV) and Nb(V) precursors via one-electron and transmetalation reactions, respectively. In the presence of azobenzene, the transient Nb(III) intermediate, prepared from Li(PNP) and NbCl3(DME) (DME = dimethoxyethane) under Ar, cleaves the N=N bond via a metal-ligand cooperative four-electron reduction to form niobium imide and phosphoranimine functionalities. Structural studies are presented and discussed for various Nb systems bearing the pincer-type framework PNP as well as the N2 and azobenzene activated products. Theoretical studies addressing the Nb-N2-Nb core in 1 are also presented.

AB - Atmospheric N2 is activated by two transient Nb(III) "(PNP)NbCl2" (PNP- = N[2-P(CHMe 2)2-4-methylphenyl]2) fragments to form the bridging diimido [(PNP)NbCl2]2(μ-N2) (1). Complex 1 can also be independently synthesized from Nb(IV) and Nb(V) precursors via one-electron and transmetalation reactions, respectively. In the presence of azobenzene, the transient Nb(III) intermediate, prepared from Li(PNP) and NbCl3(DME) (DME = dimethoxyethane) under Ar, cleaves the N=N bond via a metal-ligand cooperative four-electron reduction to form niobium imide and phosphoranimine functionalities. Structural studies are presented and discussed for various Nb systems bearing the pincer-type framework PNP as well as the N2 and azobenzene activated products. Theoretical studies addressing the Nb-N2-Nb core in 1 are also presented.

UR - https://www.scopus.com/pages/publications/33846550090

U2 - 10.1021/ic061642b

DO - 10.1021/ic061642b

M3 - Article

AN - SCOPUS:33846550090

SN - 0020-1669

VL - 45

SP - 10712

EP - 10721

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 26

ER -

Activation of atmospheric nitrogen and azobenzene N=N bond cleavage by a transient Nb(III) complex

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