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Substituent effects. Synthesis and structural characterization of group 4 metallacarboranes containing (CHCH) CBH and [o-C H(CH)]CB H ligands

Organometallics, ISSN: 0276-7333, Vol: 23, Issue: 18, Page: 4301-4307
2004
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  • Citations
    28
    • Citation Indexes
      28
  • Captures
    4

Article Description

Substituants on the carborane cage carbons affect not only bonding interactions between the group 4 metal ion and the carboranyl of the C B system but also the reactivity pattern of the resulting metal complexes. Treatment of MCI(THF) with 1 equiv of [(CHCH)C BH]Na(THF), in THF at room temperature gave the bis(carboranyl) complexes {n:n -[(CHCH)C BH]MCI(THF)}{Na(THF) } (M = Zr (1), Hf (2)). Under the same reaction conditions, interaction of TiCl(THF) with 1 equiv of [(C HCH)CB H]Na(THF) led to the isolation of a small amount of TiCl(THF) and B-substituted zwitterionic compound (CHCH) CBH(THF) (4). Reaction of 1 with 1 equiv of Li[N(SiMe)] resulted in the replacement of a Na by a Li, giving the ionic complex [n :n-{(CHCH) CBH}ZrCl-(THF)] [Li(THF)] (3). ClZr[N(SiMe)] was isolated from the reaction of 1 with excess Li-[N(SiMe) ]. An equimolar reaction between M(NEt) and (CHCH)BH afforded the monocarboranyl complexes [n-(C HCH)CB H]M(NEt)(NHEt) (M = Ti (5), Zr (6)). It is believed that the additional N(p )→M(d) interactions stabilize this type of complex. Treatment of MCl(THF) with 1 equiv of less bulky yet rigid [{o-CH(CH) }CBH]Na-(THF) generated a bent-metallocene type of complex, [{o-C H(CH)}CB H]M(THF) (M = Zr (7), Hf (8)). These metallacarboranes were all fully characterized by various spectroscopic techniques and elemental analyses. Molecular structures of 1 and 3-5 were confirmed by single-crystal X-ray analyses.

Bibliographic Details

Wai Chuen Kwong; Hoi Shan Chan; Zuowei Xie; Yong Tang

American Chemical Society (ACS)

Chemistry

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