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Issue 28, 2010
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Reactivity of Zn(ii), Mg(ii) and Al(iii) chlorides with a phosphinimine ligand: new tetrameric inverse crown ether structures

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Abstract

Reaction of [Me3SiNPPh2CH3] 1 with ZnCl2 yields the dimer [ClZn(μ-Cl)(Me3SiNPPh2CH3)]22 whereas treatment of 1 with AlCl3 in THF leads to the monomeric N adduct [Cl3Al(Me3SiNPPh2CH3)] 3. Compounds 2 and 3 were found to be thermally stable and were fully characterized by NMR spectroscopy, X-ray diffraction, and elemental analysis. On the other hand, treatment of phosphinimine 1 with nBuLi/ZnCl2 or (CH3)2CHMgCl yields the zinc and magnesium complexes [M4(Me3SiNPPh2CH2)44-O)(μ2-Cl)2] 5 (M = Zn) and 6 (M = Mg), respectively. These compounds can be considered as new examples of inverse crown ethers in which the oxygen atom is encapsulated by polar organometallic complexes in a tetrameric arrangement. In contrast, reaction of 1 with nBuLi/AlCl3 in Et2O under inert atmospheric conditions leads to the formation of the dimeric species [Cl2Al(Me3SiNPPh2CH2O)]27, which displays oxygen insertion into the C–Al bond, while the same reaction in the presence of air yields the compound [μ-(AlCl2)(NPPh2CH3)]28 with loss of ClSiMe3 and without oxygen insertion into the C–Al bond.

Graphical abstract: Reactivity of Zn(ii), Mg(ii) and Al(iii) chlorides with a phosphinimine ligand: new tetrameric inverse crown ether structures

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Supplementary files

Article information


Submitted
04 Dec 2009
Accepted
07 May 2010
First published
09 Jun 2010

Dalton Trans., 2010,39, 6441-6448
Article type
Paper

Reactivity of Zn(II), Mg(II) and Al(III) chlorides with a phosphinimine ligand: new tetrameric inverse crown ether structures

C. V. Cárdenas, M. Á. M. Hernández and J. Grévy, Dalton Trans., 2010, 39, 6441
DOI: 10.1039/B925580J

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