Facile Pyrazolylborate Ligand Degradation at Lanthanide Centers:  X-ray Crystal Structures of Pyrazolylborinate-Bridged Bimetallics

Adventitious hydrolysis of a number of different complexes with the molecular formula Ln(TpMe2)2X [TpMe2 = (HB(dmpz)3), where X is a basic anionic ligand] in various solvents, yielded crystals of highly insoluble dimers of the general formula [Ln(TpMe2)(μ-BOpMe2)]2 (1) [Ln = La, Ce, Sm; BOpMe2 = (HB...

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Published in:Inorganic chemistry 2002-12, Vol.41 (25), p.6761-6768
Main Authors: Domingos, Ângela, Elsegood, Mark R. J, Hillier, Anna C, Lin, Guanyang, Liu, Sung Ying, Lopes, Irene, Marques, Noémia, Maunder, Graham H, McDonald, Robert, Sella, Andrea, Steed, Jonathan W, Takats, Josef
Format: Article
Language:English
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Summary:Adventitious hydrolysis of a number of different complexes with the molecular formula Ln(TpMe2)2X [TpMe2 = (HB(dmpz)3), where X is a basic anionic ligand] in various solvents, yielded crystals of highly insoluble dimers of the general formula [Ln(TpMe2)(μ-BOpMe2)]2 (1) [Ln = La, Ce, Sm; BOpMe2 = (HBO(dmpz)2)2-; dmpzH = 3,5-dimethylpyrazole]. The results of several single-crystal X-ray determinations are reported. One metal nitrogen distance, that lying across from the two negatively charged bridging oxygen atoms, is 0.06 Å longer than the others, suggesting an unusual trans influence at a lanthanide center. The formation of 1 is proposed to involve the intermediacy of Ln(TpMe2)2OH formed by protonolysis with adventitious water.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic025801c