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Heteroleptic complexes of lanthanum(III) and neodymium(III) with oxygen- or nitrogen-functionalized tris(triorganosilyl)methyl ligands

Organometallics, ISSN: 0276-7333, Vol: 25, Issue: 12, Page: 2999-3006
2006
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  • Citations
    21
    • Citation Indexes
      21
  • Captures
    4

Article Description

Metathesis reactions between LaI(THF) and either 2 equiv of [(MeSi){Me(MeN)Si}C]K or 1 equiv of {(MeSi)(MeMeOSi)C(SiMeCH )}K in THF yield the heteroleptic lanthanum dialkyls [(Me-Si){Me(MeN)Si}C] LaI (3) and [{(MeSi)(MeMeOSi)C(SiMe CH)}]LaI(THF) (5), respectively. In contrast, the reaction between LaI(THF) and 2 equiv of [(MeSi){Me(MeO)Si}C]K in THF, under a variety of reaction conditions, gives a mixture of the mono- and disubstituted compounds [(MeSi)-{Me(MeO)Si}C]LaI (THF) (7) and [(MeSi){Me(MeO)Si} C]LaI(THF) (8), which cannot be separated by crystallization. The reaction between this mixture and 1 equiv of KN(SiMe) yields the heteroleptic complex [(MeSi){Me (MeO)Si}C]LaI{N(SiMe)}(THF) (9). While exact analogues of 3, 5, 8, and 9 could not be isolated for neodymium, a metathesis reaction between NdI(THF) and the lithium iodide containing potassium alkyl {(MeSi)(MeMeOSi)C(SiMe CH)}K·xLiI in THF yields the ate complex {(MeSi)(MeMeOSi)C(SiMe CH)}Nd(μ-I)Li(THF) (10). An unexpected ligand degradation is observed in the reaction between NdI(THF) and 2 equiv of [(Me Si){Me(MeO)Si}C]K in THF: this reaction yields the methoxy-bridged dimer {[(MeSi){Me (MeO)Si}C]Nd(I)(THF)(μ-OMe)} (11), via Si-O cleavage of one of the ligands. Compounds 3,5, and 8-11 have been characterized by elemental analyses and X-ray crystallography; the diamagnetic compounds 3,5,8, and 9 have additionally been characterized by NMR spectroscopy. The diastereomeric compound 5 gives a single set of resonances in its H and C{H} NMR spectra, suggesting either a rapid dynamic equilibrium between the two possible diastereomers on the NMR time scale or the formation of a single diastereomer of this compound. © 2006 American Chemical Society.

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