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Carbodiimide insertion reactions of homoleptic heavier alkaline earth amides and phosphides


Reference:

Barrett, A. G. M., Crimmin, M. R., Hill, M., Hitchcock, P. B., Lomas, S. L., Mahon, M. F. and Procopiou, P. A., 2010. Carbodiimide insertion reactions of homoleptic heavier alkaline earth amides and phosphides. Dalton Transactions, 39 (31), pp. 7393-7400.

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Official URL:

http://dx.doi.org/10.1039/c0dt00089b

Abstract

A series of homoleptic guanidinate-type complexes of the heavier alkaline earth (Ae) metals calcium and strontium have been prepared. The six-coordinate compounds [Ae{iPrNC(NPh2)CNiPr} 2(THF)2] (Ae = Ca and Sr) were synthesised through reactions of the appropriate THF-solvated hexamethyldisilazide [Ae{N(SiMe 3)2}2(THF)2] with two molar equivalents of diphenylamine and 1,3-di-iso-propylcarbodiimide. Both compounds were shown to crystallise with a cisoid arrangement of the two THF molecules at the metal centres. In contrast, the (Me3Si)2N-substituted calcium guanidinate, [Ca{CyNC{N(SiMe3)2}CNCy} 2(THF)2], contains two coordinated THF molecules with a trans disposition. Further reactions of the free amidine [{(2-FC 6H4)N}C(NHiPr)2] with either [Ca{N(SiMe3)2}2(THF)2] or its dimeric unsolvated analogue provided monomeric or dimeric derivatives respectively in which the ligands had tautomerised to an anisobidentate form. A further reaction of the phosphaguanidine [CyNC(PPh2)N(H)Cy] with [Sr{N(SiMe3)2}2(THF)2] provided the first example of a phosphaguanidinate complex of this heavier alkaline earth metal. This compound has also been characterised in the solid state and shown to exist with a transoid configuration of the coordinated THF molecules.

Details

Item Type Articles
CreatorsBarrett, A. G. M., Crimmin, M. R., Hill, M., Hitchcock, P. B., Lomas, S. L., Mahon, M. F. and Procopiou, P. A.
DOI10.1039/c0dt00089b
DepartmentsFaculty of Science > Chemistry
RefereedYes
StatusPublished
ID Code20330

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