Catalytic formation of ammonia from molecular dinitrogen by use of dinitrogen-bridged dimolybdenum-dinitrogen complexes bearing pnp-pincer ligands: Remarkable effect of substituent at pnp-pincer ligand

Shogo Kuriyama, Kazuya Arashiba, Kazunari Nakajima, Hiromasa Tanaka, Nobuaki Kamaru, Kazunari Yoshizawa, Yoshiaki Nishibayashi

Research output: Contribution to journalArticle

93 Citations (Scopus)

Abstract

A series of dinitrogen-bridged dimolybdenum-dinitrogen complexes bearing 4-substituted PNP-pincer ligands are synthesized by the reduction of the corresponding molybdenum trichloride complexes under 1 atm of molecular dinitrogen. In accordance with a theoretical study, the catalytic activity is enhanced by the introduction of an electron-donating group to the pyridine ring of PNP-pincer ligand, and the complex bearing 4-methoxy-substituted PNP-pincer ligands is found to work as the most effective catalyst, where 52 equiv of ammonia are produced based on the catalyst (26 equiv of ammonia based on each molybdenum atom of the catalyst), together with molecular dihydrogen as a side-product. Time profiles for the catalytic reactions indicate that the rates of the formation of ammonia and molecular dihydrogen depend on the nature of the substituent on the PNP-pincer ligand of the complexes. The formation of ammonia and molecular dihydrogen is complementary in the reaction system.

Original languageEnglish
Pages (from-to)9719-9731
Number of pages13
JournalJournal of the American Chemical Society
Volume136
Issue number27
DOIs
Publication statusPublished - Jul 9 2014

Fingerprint

Bearings (structural)
Ammonia
Ligands
Molybdenum
Catalysts
Pyridine
Catalyst activity
Theoretical Models
Electrons
Atoms

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Catalytic formation of ammonia from molecular dinitrogen by use of dinitrogen-bridged dimolybdenum-dinitrogen complexes bearing pnp-pincer ligands : Remarkable effect of substituent at pnp-pincer ligand. / Kuriyama, Shogo; Arashiba, Kazuya; Nakajima, Kazunari; Tanaka, Hiromasa; Kamaru, Nobuaki; Yoshizawa, Kazunari; Nishibayashi, Yoshiaki.

In: Journal of the American Chemical Society, Vol. 136, No. 27, 09.07.2014, p. 9719-9731.

Research output: Contribution to journalArticle

@article{4185798fb72f41d6ab1091975a2abf2f,
title = "Catalytic formation of ammonia from molecular dinitrogen by use of dinitrogen-bridged dimolybdenum-dinitrogen complexes bearing pnp-pincer ligands: Remarkable effect of substituent at pnp-pincer ligand",
abstract = "A series of dinitrogen-bridged dimolybdenum-dinitrogen complexes bearing 4-substituted PNP-pincer ligands are synthesized by the reduction of the corresponding molybdenum trichloride complexes under 1 atm of molecular dinitrogen. In accordance with a theoretical study, the catalytic activity is enhanced by the introduction of an electron-donating group to the pyridine ring of PNP-pincer ligand, and the complex bearing 4-methoxy-substituted PNP-pincer ligands is found to work as the most effective catalyst, where 52 equiv of ammonia are produced based on the catalyst (26 equiv of ammonia based on each molybdenum atom of the catalyst), together with molecular dihydrogen as a side-product. Time profiles for the catalytic reactions indicate that the rates of the formation of ammonia and molecular dihydrogen depend on the nature of the substituent on the PNP-pincer ligand of the complexes. The formation of ammonia and molecular dihydrogen is complementary in the reaction system.",
author = "Shogo Kuriyama and Kazuya Arashiba and Kazunari Nakajima and Hiromasa Tanaka and Nobuaki Kamaru and Kazunari Yoshizawa and Yoshiaki Nishibayashi",
year = "2014",
month = "7",
day = "9",
doi = "10.1021/ja5044243",
language = "English",
volume = "136",
pages = "9719--9731",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "27",

}

TY - JOUR

T1 - Catalytic formation of ammonia from molecular dinitrogen by use of dinitrogen-bridged dimolybdenum-dinitrogen complexes bearing pnp-pincer ligands

T2 - Remarkable effect of substituent at pnp-pincer ligand

AU - Kuriyama, Shogo

AU - Arashiba, Kazuya

AU - Nakajima, Kazunari

AU - Tanaka, Hiromasa

AU - Kamaru, Nobuaki

AU - Yoshizawa, Kazunari

AU - Nishibayashi, Yoshiaki

PY - 2014/7/9

Y1 - 2014/7/9

N2 - A series of dinitrogen-bridged dimolybdenum-dinitrogen complexes bearing 4-substituted PNP-pincer ligands are synthesized by the reduction of the corresponding molybdenum trichloride complexes under 1 atm of molecular dinitrogen. In accordance with a theoretical study, the catalytic activity is enhanced by the introduction of an electron-donating group to the pyridine ring of PNP-pincer ligand, and the complex bearing 4-methoxy-substituted PNP-pincer ligands is found to work as the most effective catalyst, where 52 equiv of ammonia are produced based on the catalyst (26 equiv of ammonia based on each molybdenum atom of the catalyst), together with molecular dihydrogen as a side-product. Time profiles for the catalytic reactions indicate that the rates of the formation of ammonia and molecular dihydrogen depend on the nature of the substituent on the PNP-pincer ligand of the complexes. The formation of ammonia and molecular dihydrogen is complementary in the reaction system.

AB - A series of dinitrogen-bridged dimolybdenum-dinitrogen complexes bearing 4-substituted PNP-pincer ligands are synthesized by the reduction of the corresponding molybdenum trichloride complexes under 1 atm of molecular dinitrogen. In accordance with a theoretical study, the catalytic activity is enhanced by the introduction of an electron-donating group to the pyridine ring of PNP-pincer ligand, and the complex bearing 4-methoxy-substituted PNP-pincer ligands is found to work as the most effective catalyst, where 52 equiv of ammonia are produced based on the catalyst (26 equiv of ammonia based on each molybdenum atom of the catalyst), together with molecular dihydrogen as a side-product. Time profiles for the catalytic reactions indicate that the rates of the formation of ammonia and molecular dihydrogen depend on the nature of the substituent on the PNP-pincer ligand of the complexes. The formation of ammonia and molecular dihydrogen is complementary in the reaction system.

UR - http://www.scopus.com/inward/record.url?scp=84904012648&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84904012648&partnerID=8YFLogxK

U2 - 10.1021/ja5044243

DO - 10.1021/ja5044243

M3 - Article

AN - SCOPUS:84904012648

VL - 136

SP - 9719

EP - 9731

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 27

ER -