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Thorman JL, Young VG, Boyd PD, et al. Atom transfer reactions of (TTP)Ti(eta 2-3-hexyne): synthesis and molecular structure of trans-(TTP)Ti[OP(Oct)3]2. Inorg Chem. 2001;40(3):499-506doi: 10.1021/ic0003426.
Thorman, J. L., Young, V. G., Boyd, P. D., Guzei, I. A., & Woo, L. K. (2001). Atom transfer reactions of (TTP)Ti(eta 2-3-hexyne): synthesis and molecular structure of trans-(TTP)Ti[OP(Oct)3]2. Inorganic chemistry, 40(3), 499-506. https://doi.org/10.1021/ic0003426
Thorman, J L, et al. "Atom transfer reactions of (TTP)Ti(eta 2-3-hexyne): synthesis and molecular structure of trans-(TTP)Ti[OP(Oct)3]2." Inorganic chemistry vol. 40,3 (2001): 499-506. doi: https://doi.org/10.1021/ic0003426
Thorman JL, Young VG, Boyd PD, Guzei IA, Woo LK. Atom transfer reactions of (TTP)Ti(eta 2-3-hexyne): synthesis and molecular structure of trans-(TTP)Ti[OP(Oct)3]2. Inorg Chem. 2001 Jan 29;40(3):499-506. doi: 10.1021/ic0003426. PMID: 11209607.
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Inorg Chem. 2001 Jan 29;40(3):499-506. doi: 10.1021/ic0003426.

Atom transfer reactions of (TTP)Ti(eta 2-3-hexyne): synthesis and molecular structure of trans-(TTP)Ti[OP(Oct)3]2.

Inorganic chemistry

J L Thorman, V G Young, P D Boyd, I A Guzei, L K Woo

Affiliations

  1. Department of Chemistry, Iowa State University, Ames, Iowa 50011-3111, USA.

PMID: 11209607 DOI: 10.1021/ic0003426

Abstract

Atom and group transfer reactions were found to occur between heterocumulenes and (TTP)Ti(eta 2-3-hexyne), 1 (TTP = meso-5,10,15,20-tetra-p-tolylporphyrinato dianion). The imido derivatives (TTP)Ti=NR (R = iPr, 2; tBu, 3) were produced upon treatment of complex 1 with iPrN=C=NiPr, iPrNCO, or tBuNCO. Reactions between complex 1 and CS2, tBuNCS, or tBuNCSe afforded the chalcogenido complexes, (TTP)Ti=Ch (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(eta 2-3-hexyne) readily abstracts oxygen from epoxides and sulfoxides, the reaction between 1 and O=P(Oct)3 did not result in oxygen atom transfer. Instead, the paramagnetic titanium(II) derivative (TTP)Ti[O=P(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) A and Ti-O-P angle of 138.43(10) degrees. Estimates of Ti=O, Ti=S, Ti=Se, and Ti=NR bond strengths are discussed.

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