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Atom Transfer Reactions of (TTP)Ti(η2-3-hexyne): Synthesis and Molecular Structure of trans-(TTP)Ti[OP(Oct)3]2
Inorganic Chemistry
  • Joseph Lyndon Thorman, Iowa State University
  • Victor G. Young, Jr., University of Minnesota - Twin Cities
  • Peter D. W. Boyd, University of Auckland
  • Ilia A. Guzei, Iowa State University
  • L. Keith Woo, Iowa State University
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Atom and group transfer reactions were found to occur between heterocumulenes and (TTP)Ti(η2-3-hexyne), 1 (TTP = meso-5,10,15,20-tetra-p-tolylporphyrinato dianion). The imido derivatives (TTP)TiNR (R = iPr, 2; tBu, 3) were produced upon treatment of complex1 with iPrNCNiPr, iPrNCO, or tBuNCO. Reactions between complex 1 and CS2, tBuNCS, or tBuNCSe afforded the chalcogenido complexes, (TTP)TiCh (Ch = Se, 4; S, 5). Treatment of complex 1 with 2 equiv of PEt3 yielded the bis(phosphine) complex, (TTP)Ti(PEt3)2, 6. Although (TTP)Ti(η2-3-hexyne) readily abstracts oxygen from epoxides and sulfoxides, the reaction between 1 and OP(Oct)3 did not result in oxygen atom transfer. Instead, the paramagnetic titanium(II) derivative (TTP)Ti[OP(Oct)3]2, 7, was formed. The molecular structure of complex 7 was determined by single-crystal X-ray diffraction:  Ti−O distance 2.080(2) Å and Ti−O−P angle of 138.43(10)°. Estimates of TiO, TiS, TiSe, and TiNR bond strengths are discussed.

Reprinted (adapted) with permission from Inorganic Chemistry 40 (2001): 499, doi:10.1021/ic0003426. Copyright 2001 American Chemical Society.

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American Chemical Society
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Joseph Lyndon Thorman, Victor G. Young, Peter D. W. Boyd, Ilia A. Guzei, et al.. "Atom Transfer Reactions of (TTP)Ti(η2-3-hexyne): Synthesis and Molecular Structure of trans-(TTP)Ti[OP(Oct)3]2" Inorganic Chemistry Vol. 40 Iss. 3 (2000) p. 499 - 506
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