Biphenolate phosphine complexes of tantalum

Lan Chang Liang, Liang Chien Cheng, Tzung Ling Tsai, Ching Han Hu, Wen Hsin Guo

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Abstract

The preparation and structural characterization of tantalum complexes supported by 2,2′-phenylphosphino-bis(4,6-di-terf-butylphenolate) ([OPO]2-) are described. The reaction of Li2[OPO] with TaCI2, regardless of the molar ratio employed, in diethyl ether at -35 °C led to high-yield isolation of yellow crystalline [OPO] 2TaCI. Alkylation of [OPO]2TaCI with MeMgBr or EtMgCI in diethyl ether at - 35 °C generated the corresponding alkyl complexes [OPO]2TaR (R = Me, Et). Thermolysis of [OPO]2TaEt in benzene led to quantitative formation of [OPO]2TaH, which could also be prepared by treatment of [OPO]2TaCI with LiHBEt3 in diethyl ether at -35 °C. Hydrolysis of [OPO]2TaCI or [OPO] 2TaR (R = H, Me, Et) generated [OPO]2TaOH. The reaction of [OPO]2TaQH with Me3SiCI in diethyl ether at room temperature afforded quantitatively [OPO]2TaCI. The solution structures of these complexes were all characterized by multinuclear NMR spectroscopy. The solid-state structures of [OPO]2TaCI, [OPO] 2TaH, and [OPO]2TaOH were determined by X-ray crystallography. The spectroscopic and crystallographic data are all indicative of the coordination of both phosphorus donors to tantalum in these 7-coordinate complexes. Interestingly, the structure of [OPO]2TaH is markedly different from those of [OPO]2TaX (X = Cl, OH, Me, Et) on the basis of NMR and X-ray studies. Density functional theory computations reveal that the hydride structure found by X-ray crystallography Is lower in energy by about 7 kcal/mol than that analogous to the established X-ray structures of [OPO] 2TaCI and [OPO]2TaOH.

Original languageEnglish
Pages (from-to)5697-5703
Number of pages7
JournalInorganic Chemistry
Volume48
Issue number13
DOIs
Publication statusPublished - 2009 Jul 6

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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    Liang, L. C., Cheng, L. C., Tsai, T. L., Hu, C. H., & Guo, W. H. (2009). Biphenolate phosphine complexes of tantalum. Inorganic Chemistry, 48(13), 5697-5703. https://doi.org/10.1021/ic802125z