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Complexes of the heavier alkaline earth metals Ca, Sr, and Ba with O-functionalized phosphanide ligands

Lookup NU author(s): Stuart Blair, Dr Keith Izod, Emeritus Professor Bill CleggORCiD, Dr Ross Harrington


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Metathesis reactions between either SrI2 or BaI2 and 2 equiv of the potassium phosphanide [{(Me3Si)2CH}-(C 6H4-2-OMe)P]K yield, after recrystallization, the complexes [{([Me3Si]2CH)(C6H 4-2-OMe)P}2M(THF)n] [M = Sr, n = 2 (5); Ba, n = 3 (6)]. Similar metathesis reactions between MI2 and 2 equiv of the more sterically demanding potassium phosphanide [{(Me3Si) 2CH}(C6H3-2-OMe-3-Me)P]K yield the chemically isostructural complexes [{([Me3Si]2CH)(C6H 3-2-OMe-3-Me)P}2M(THF)2] [M = Ca (9), Sr (7), Ba (8)]. Compounds 5-9 have been characterized by multi-element NMR spectroscopy and X-ray crystallography. Complex 9 is thermally unstable and decomposes at room temperature to give the tertiary phosphane {(Me3Si) 2CH}(C6H3-2-OMe-3-Me)P(Me) and an unidentified Ca-containing product. Compounds 5 and 6 also decompose at elevated temperatures to give the corresponding tertiary phosphane {(Me3Si) 2CH}(C6H4-2-OMe)P(Me) and intractable metal-containing products. The decomposition of 5, 6, and 9 suggests that these compounds undergo an intramolecular methyl migration from the O atom in one phosphanide ligand to the P atom of an adjacent phosphanide ligand to give species containing dianionic alkoxo-phosphanide ligands.

Publication metadata

Author(s): Blair S, Izod K, Clegg W, Harrington RW

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2004

Volume: 43

Issue: 26

Pages: 8526-8531

ISSN (print): 0020-1669

ISSN (electronic): 1520-510X

Publisher: American Chemical Society


DOI: 10.1021/ic048978a


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