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 language | English (US) |
|---|---|
| Pages (from-to) | 188-198 |
| Number of pages | 11 |
| Journal | Organometallics |
| Volume | 20 |
| Issue number | 1 |
| State | Published - Jan 8 2001 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
Cite this
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 journal › Article
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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.
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M3 - Article
AN - SCOPUS:0035124647
VL - 20
SP - 188
EP - 198
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 1
ER -