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Lookup NU author(s): Stuart Blair, Dr Keith Izod, Professor William Clegg, 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.
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
URL: http://dx.doi.org/10.1021/ic048978a
DOI: 10.1021/ic048978a
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