Synthesis and ligand modification chemistry of a molybdenum dinitrogen complex: Redox and chemical activity of a bis-(imino)pyridine ligand

Grant W. Margulieux; Zoë R. Turner; Paul J. Chirik

doi:10.1002/anie.201408725

Synthesis and ligand modification chemistry of a molybdenum dinitrogen complex: Redox and chemical activity of a bis-(imino)pyridine ligand

Grant W. Margulieux, Zoë R. Turner, Paul J. Chirik

Chemistry

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

62 Scopus citations

Abstract

The bis(imino)pyridine 2,6-(2,6-iPr₂-C₆H₃N=CPh)₂-C₅H₃N (^iPrBPDI) molybdenum dinitrogen complex, [{(^iPrBPDI)Mo(N₂)}₂(μ₂,≠¹,≠¹-N₂)] has been prepared and contains both weakly (terminal) and modestly (bridging) activated N₂ ligands. Addition of ammonia resulted in sequential N-H bond activations, thus forming bridging parent imido (μ-NH) ligands with concomitant reduction of one of the imines of the supporting chelate. Using primary and secondary amines, model intermediates have been isolated that highlight the role of metal-ligand cooperativity in NH₃ oxidation.

Original language	English (US)
Pages (from-to)	14211-14215
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	53
Issue number	51
DOIs	https://doi.org/10.1002/anie.201408725
State	Published - Dec 15 2014

All Science Journal Classification (ASJC) codes

General Chemistry
Catalysis

Keywords

Cooperative effects
Ligand effects
Molybdenum
Nitrogen
Oxidation

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title = "Synthesis and ligand modification chemistry of a molybdenum dinitrogen complex: Redox and chemical activity of a bis-(imino)pyridine ligand",

abstract = "The bis(imino)pyridine 2,6-(2,6-iPr2-C6H3N=CPh)2-C5H3N (iPrBPDI) molybdenum dinitrogen complex, [{(iPrBPDI)Mo(N2)}2(μ2,≠1,≠1-N2)] has been prepared and contains both weakly (terminal) and modestly (bridging) activated N2 ligands. Addition of ammonia resulted in sequential N-H bond activations, thus forming bridging parent imido (μ-NH) ligands with concomitant reduction of one of the imines of the supporting chelate. Using primary and secondary amines, model intermediates have been isolated that highlight the role of metal-ligand cooperativity in NH3 oxidation.",

keywords = "Cooperative effects, Ligand effects, Molybdenum, Nitrogen, Oxidation",

author = "Margulieux, {Grant W.} and Turner, {Zo{\"e} R.} and Chirik, {Paul J.}",

note = "Publisher Copyright: {\textcopyright} 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2014",

month = dec,

day = "15",

doi = "10.1002/anie.201408725",

language = "English (US)",

volume = "53",

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journal = "Angewandte Chemie - International Edition",

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T1 - Synthesis and ligand modification chemistry of a molybdenum dinitrogen complex

T2 - Redox and chemical activity of a bis-(imino)pyridine ligand

AU - Margulieux, Grant W.

AU - Turner, Zoë R.

AU - Chirik, Paul J.

PY - 2014/12/15

Y1 - 2014/12/15

N2 - The bis(imino)pyridine 2,6-(2,6-iPr2-C6H3N=CPh)2-C5H3N (iPrBPDI) molybdenum dinitrogen complex, [{(iPrBPDI)Mo(N2)}2(μ2,≠1,≠1-N2)] has been prepared and contains both weakly (terminal) and modestly (bridging) activated N2 ligands. Addition of ammonia resulted in sequential N-H bond activations, thus forming bridging parent imido (μ-NH) ligands with concomitant reduction of one of the imines of the supporting chelate. Using primary and secondary amines, model intermediates have been isolated that highlight the role of metal-ligand cooperativity in NH3 oxidation.

AB - The bis(imino)pyridine 2,6-(2,6-iPr2-C6H3N=CPh)2-C5H3N (iPrBPDI) molybdenum dinitrogen complex, [{(iPrBPDI)Mo(N2)}2(μ2,≠1,≠1-N2)] has been prepared and contains both weakly (terminal) and modestly (bridging) activated N2 ligands. Addition of ammonia resulted in sequential N-H bond activations, thus forming bridging parent imido (μ-NH) ligands with concomitant reduction of one of the imines of the supporting chelate. Using primary and secondary amines, model intermediates have been isolated that highlight the role of metal-ligand cooperativity in NH3 oxidation.

KW - Cooperative effects

KW - Ligand effects

KW - Molybdenum

KW - Nitrogen

KW - Oxidation

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ER -

Synthesis and ligand modification chemistry of a molybdenum dinitrogen complex: Redox and chemical activity of a bis-(imino)pyridine ligand

Abstract

All Science Journal Classification (ASJC) codes

Keywords

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