Carbon Monoxide Reduction by Sixteen Electron d-Zero Tantalum Complexes. Acrylonitrile Cyclodimerization by Tris(triphenylphosphine) Tetramethylene Ni(II)

Citation

Berg, Beckie E. (1979) Carbon Monoxide Reduction by Sixteen Electron d-Zero Tantalum Complexes. Acrylonitrile Cyclodimerization by Tris(triphenylphosphine) Tetramethylene Ni(II). Master's thesis, California Institute of Technology. doi:10.7907/qqt5-e721. https://resolver.caltech.edu/CaltechTHESIS:04072010-082613027

Abstract

[Part I] The sixteen electon, d-zero complexes Ta(COT)Me_3 and (η^5-C_5Me_5)Ta(C_3H_5)Me_3 were prepared and treated with carbon monoxide. The prep of Ta(COT) Me_3 gave irreproducibly small yields and upon treatment with CO paramagnetic material was observed. The prep of (η^5-C_5Me_5)Ta(C_3H_5)Me_3 resulted in yellow crystals in a red oil and these could not be separated. (η ^5C_5Me_5)Ta(C_3H_4Me)Me_3 was then made. This complex decomposes to the trimethylene methane species (η^5-C_5Me_5)Ta(C_3H_3Me)Me_2, and upon treatment with CO gave an unknown white solid product. [Part II] Tris(triphenylphoshine) tetramethylene Ni(II) was made and treated with acrylonitrile. 1, 2 dicyanocyclobutane was produced in a cis:trans mixture of 45:55 and was isolated by preparative GC. The product was rarely observed and the reaction of nickel metallocycle with acrylonitrile was not catalyzed by acid, base, or Ni(O).

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