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Issue 29, 2010
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Selective ammonolysis of half-sandwich rare-earth metal dialkyl and polyhydride complexes: synthesis of polyamido rare-earth complexes having novel structures

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Abstract

The scandium dialkyl complex [Cp′Sc(CH2SiMe3)2(THF)] (1-Sc, Cp′ = C5Me4SiMe3) reacts rapidly with ammonia at room temperature to afford selectively a trinuclear hexaamido complex [Cp′Sc(μ-NH2)2]3 (3-Sc) with release of SiMe4. The reaction of the lutetium dialkyl complex [Cp′Lu(CH2SiMe3)2(THF)] (1-Lu) with ammonia under the same conditions gives the analogous hexaamido Lu complex [Cp′Lu(μ-NH2)2]3 (3-Lu) as a major product (92%) together with a tetranuclear octaamido complex [Cp′Lu(μ-NH2)2]4 (4-Lu) as a minor product (8%). In contrast, reaction of tetranuclear rare-earth metal octahydride complexes [Cp′Ln(μ-H)2]4(THF) (Ln = Y (2-Y), Lu (2-Lu)) with ammonia under similar conditions yields selectively the heptaamido/monohydrido complexes [(Cp′Ln)4(μ-NH2)63-NH2)(μ4-H)] (Ln = Y (5-Y), Lu (5-Lu)), in which a μ4-H ligand remains at the center of the tetrahedral metal framework. Exposure of heptaamido/monohydrido complex 5-Lu to an ammonia atmosphere at room temperature for a long time (two days) affords the octaamido complex 4-Lu quantitatively. The molecular structures of 3-Sc, 3-Lu, 4-Lu, 5-Y, and 5-Lu have been determined by X-ray analyses.

Graphical abstract: Selective ammonolysis of half-sandwich rare-earth metal dialkyl and polyhydride complexes: synthesis of polyamido rare-earth complexes having novel structures

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Supplementary files

Article information


Submitted
19 Feb 2010
Accepted
16 Apr 2010
First published
02 Jun 2010

Dalton Trans., 2010,39, 6858-6863
Article type
Paper

Selective ammonolysis of half-sandwich rare-earth metal dialkyl and polyhydride complexes: synthesis of polyamido rare-earth complexes having novel structures

T. Shima and Z. Hou, Dalton Trans., 2010, 39, 6858
DOI: 10.1039/C0DT00006J

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