Syntheses, structures, and reactivities of f heterobimetallic bridging dinitrogen complexes containing group 6 and group 4 or 5 transition metals

Hiroshige Ishino, Tatsuya Nagano, Shigeki Kuwata, Youhei Yokobayashi, Youichi Ishii, Masanobu Hidai, Yasushi Mizobe

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

A series of heterobimetallic dinitrogen complexes containing group 6 and group 4 or 5 transition metals were synthesized by the reaction of the tungsten or molybdenum dinitrogen complexes cz's-[W(N2)2(PMe2Ph)4] (1) and irans-[M(N2)2(dppe)2] (2) (M = W, Mo) with group . 4 or group 5 compounds such as [CpTiCl3], [Cp2M'Cl2] (M' = Ti, Zr, Hf), or [Cp'M'Cl4] (Cp' = Cp, Cp* M' = Nb, Ta). Crystallographic studies of the complexes thus obtained including [WCl(PMe2Ph)4(H-N2)TiCpCl2] and [WCl(PMe2Ph)4CH-N2)NbCpCl3] revealed that the M-N- : N-M' core is essentially linear, and the N-N bond is regarded to have the formal bond order of 2. Several -N2 complexes with methyl ligands at the group 4 or 5 metal center were also obtained through the reaction of dinitrogen complexes 1 and 2a (M = W) with the methyl complexes [Cp2ZrMeCl], [TaMeaCl2], and [NbMe2Cl3]. The reaction of the complex [WCl(dppe)2(H-N2)TiCpCl2] with Li2S5: afforded the ?/2-pentasulfido complex [WCl(dppe)2(N2)TiCpS5], where the ?/2-Ss ligand forms a six-membered chelate ring with the chair conformation. Protonation of the -N2 complexes having PMe2Ph ligands gave NHs in moderate yield, concurrent with the formation of a small amo'unt of NH2NH2.

Original languageEnglish (US)
Pages (from-to)188-198
Number of pages11
JournalOrganometallics
Volume20
Issue number1
StatePublished - Jan 8 2001
Externally publishedYes

Fingerprint

Transition metals
reactivity
transition metals
Ligands
synthesis
Tungsten
Molybdenum
Protonation
ligands
Conformations
Metals
chelates
seats
molybdenum
tungsten
rings
metals

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Ishino, H., Nagano, T., Kuwata, S., Yokobayashi, Y., Ishii, Y., Hidai, M., & Mizobe, Y. (2001). Syntheses, structures, and reactivities of f heterobimetallic bridging dinitrogen complexes containing group 6 and group 4 or 5 transition metals. Organometallics, 20(1), 188-198.

Syntheses, structures, and reactivities of f heterobimetallic bridging dinitrogen complexes containing group 6 and group 4 or 5 transition metals. / Ishino, Hiroshige; Nagano, Tatsuya; Kuwata, Shigeki; Yokobayashi, Youhei; Ishii, Youichi; Hidai, Masanobu; Mizobe, Yasushi.

In: Organometallics, Vol. 20, No. 1, 08.01.2001, p. 188-198.

Research output: Contribution to journalArticle

Ishino, H, Nagano, T, Kuwata, S, Yokobayashi, Y, Ishii, Y, Hidai, M & Mizobe, Y 2001, 'Syntheses, structures, and reactivities of f heterobimetallic bridging dinitrogen complexes containing group 6 and group 4 or 5 transition metals', Organometallics, vol. 20, no. 1, pp. 188-198.
Ishino, Hiroshige ; Nagano, Tatsuya ; Kuwata, Shigeki ; Yokobayashi, Youhei ; Ishii, Youichi ; Hidai, Masanobu ; Mizobe, Yasushi. / Syntheses, structures, and reactivities of f heterobimetallic bridging dinitrogen complexes containing group 6 and group 4 or 5 transition metals. In: Organometallics. 2001 ; Vol. 20, No. 1. pp. 188-198.
@article{1908a946f40c438c820f8eb67b3db19c,
title = "Syntheses, structures, and reactivities of f heterobimetallic bridging dinitrogen complexes containing group 6 and group 4 or 5 transition metals",
abstract = "A series of heterobimetallic dinitrogen complexes containing group 6 and group 4 or 5 transition metals were synthesized by the reaction of the tungsten or molybdenum dinitrogen complexes cz's-[W(N2)2(PMe2Ph)4] (1) and irans-[M(N2)2(dppe)2] (2) (M = W, Mo) with group . 4 or group 5 compounds such as [CpTiCl3], [Cp2M'Cl2] (M' = Ti, Zr, Hf), or [Cp'M'Cl4] (Cp' = Cp, Cp* M' = Nb, Ta). Crystallographic studies of the complexes thus obtained including [WCl(PMe2Ph)4(H-N2)TiCpCl2] and [WCl(PMe2Ph)4CH-N2)NbCpCl3] revealed that the M-N- : N-M' core is essentially linear, and the N-N bond is regarded to have the formal bond order of 2. Several -N2 complexes with methyl ligands at the group 4 or 5 metal center were also obtained through the reaction of dinitrogen complexes 1 and 2a (M = W) with the methyl complexes [Cp2ZrMeCl], [TaMeaCl2], and [NbMe2Cl3]. The reaction of the complex [WCl(dppe)2(H-N2)TiCpCl2] with Li2S5: afforded the ?/2-pentasulfido complex [WCl(dppe)2(N2)TiCpS5], where the ?/2-Ss ligand forms a six-membered chelate ring with the chair conformation. Protonation of the -N2 complexes having PMe2Ph ligands gave NHs in moderate yield, concurrent with the formation of a small amo'unt of NH2NH2.",
author = "Hiroshige Ishino and Tatsuya Nagano and Shigeki Kuwata and Youhei Yokobayashi and Youichi Ishii and Masanobu Hidai and Yasushi Mizobe",
year = "2001",
month = "1",
day = "8",
language = "English (US)",
volume = "20",
pages = "188--198",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "1",

}

TY - JOUR

T1 - Syntheses, structures, and reactivities of f heterobimetallic bridging dinitrogen complexes containing group 6 and group 4 or 5 transition metals

AU - Ishino, Hiroshige

AU - Nagano, Tatsuya

AU - Kuwata, Shigeki

AU - Yokobayashi, Youhei

AU - Ishii, Youichi

AU - Hidai, Masanobu

AU - Mizobe, Yasushi

PY - 2001/1/8

Y1 - 2001/1/8

N2 - A series of heterobimetallic dinitrogen complexes containing group 6 and group 4 or 5 transition metals were synthesized by the reaction of the tungsten or molybdenum dinitrogen complexes cz's-[W(N2)2(PMe2Ph)4] (1) and irans-[M(N2)2(dppe)2] (2) (M = W, Mo) with group . 4 or group 5 compounds such as [CpTiCl3], [Cp2M'Cl2] (M' = Ti, Zr, Hf), or [Cp'M'Cl4] (Cp' = Cp, Cp* M' = Nb, Ta). Crystallographic studies of the complexes thus obtained including [WCl(PMe2Ph)4(H-N2)TiCpCl2] and [WCl(PMe2Ph)4CH-N2)NbCpCl3] revealed that the M-N- : N-M' core is essentially linear, and the N-N bond is regarded to have the formal bond order of 2. Several -N2 complexes with methyl ligands at the group 4 or 5 metal center were also obtained through the reaction of dinitrogen complexes 1 and 2a (M = W) with the methyl complexes [Cp2ZrMeCl], [TaMeaCl2], and [NbMe2Cl3]. The reaction of the complex [WCl(dppe)2(H-N2)TiCpCl2] with Li2S5: afforded the ?/2-pentasulfido complex [WCl(dppe)2(N2)TiCpS5], where the ?/2-Ss ligand forms a six-membered chelate ring with the chair conformation. Protonation of the -N2 complexes having PMe2Ph ligands gave NHs in moderate yield, concurrent with the formation of a small amo'unt of NH2NH2.

AB - A series of heterobimetallic dinitrogen complexes containing group 6 and group 4 or 5 transition metals were synthesized by the reaction of the tungsten or molybdenum dinitrogen complexes cz's-[W(N2)2(PMe2Ph)4] (1) and irans-[M(N2)2(dppe)2] (2) (M = W, Mo) with group . 4 or group 5 compounds such as [CpTiCl3], [Cp2M'Cl2] (M' = Ti, Zr, Hf), or [Cp'M'Cl4] (Cp' = Cp, Cp* M' = Nb, Ta). Crystallographic studies of the complexes thus obtained including [WCl(PMe2Ph)4(H-N2)TiCpCl2] and [WCl(PMe2Ph)4CH-N2)NbCpCl3] revealed that the M-N- : N-M' core is essentially linear, and the N-N bond is regarded to have the formal bond order of 2. Several -N2 complexes with methyl ligands at the group 4 or 5 metal center were also obtained through the reaction of dinitrogen complexes 1 and 2a (M = W) with the methyl complexes [Cp2ZrMeCl], [TaMeaCl2], and [NbMe2Cl3]. The reaction of the complex [WCl(dppe)2(H-N2)TiCpCl2] with Li2S5: afforded the ?/2-pentasulfido complex [WCl(dppe)2(N2)TiCpS5], where the ?/2-Ss ligand forms a six-membered chelate ring with the chair conformation. Protonation of the -N2 complexes having PMe2Ph ligands gave NHs in moderate yield, concurrent with the formation of a small amo'unt of NH2NH2.

UR - http://www.scopus.com/inward/record.url?scp=0035124647&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0035124647&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0035124647

VL - 20

SP - 188

EP - 198

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 1

ER -