Atom Transfer Reactions of (TTP)Ti(η2-3-hexyne): Synthesis and Molecular Structure of trans-(TTP)Ti[OP(Oct)3]2Inorganic Chemistry
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AbstractAtom 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.
Copyright OwnerAmerican Chemical Society
Citation InformationJoseph 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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