Chemical nitrogen fixation by using molybdenum and tungsten complexes*
Masanobu Hidai and Yasushi Mizobe
Department of Materials Science and Technology, Faculty
of Industrial Science and Technology, Science University of Tokyo, Noda,
Chiba 278-8510, Japan, and Institute of Industrial Science, The University
of Tokyo, Roppongi, Minato-ku, Tokyo, 106-8558, Japan
Abstract: Dinitrogen complex cis-[W (N2) 2 (PMe2Ph)
4] reacts with an excess of acidic dihydrogen complexes such as
trans-[RuCl (h2-H2) (dppe) 2]BF4
(dppe = 1,2-bis (diphenylphosphino) ethane) at 55 °C under 1 atm
of H2 to form ammonia in moderate yield. The reaction is
presumed to proceed through nucleophilic attack of the remote nitrogen
of the coordinated dinitrogen on the dihydrogen ligand. The coordinated
dinitrogen is also protonated by treatment with hydrosulfido-bridged
dinuclear complexes such as [Cp*Ir (m-SH) 3IrCp*]Cl (Cp* =
h5-C5Me5) to afford ammonia. On the
other hand, the synthetic cycle for the formation of pyrrole and N-aminopyrrole
from dinitrogen and 2,5-dimethoxytetrahydrofuran has been established
starting from dinitrogen complexes of the type trans-[M (N2) 2 (dppe) 2
] (M = Mo, W).
* Lecture presented at the XIXth International Conference
on Organometallic Chemistry (XIX ICOMC) , Shanghai, China, 23-28 July
2000. Other presentations are published in this issue, pp. 205-376.
** Corresponding author
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