Atom transfer reactions of (TTP)Ti(n2-3-hexyne): Synthesis and molecular structure of trans-(TTP)Ti[OP(Oct)3]2

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

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Abstract

Atom and group transfer reactions were found to occur between heterocumulenes and (TTP)Ti(n2-3-hexyne), 1 (TTP = meso-5,10,15,20-tetra-p-toly]porphyrinato dianion). The imido derivatives (TTP)Ti=NR (R = ′Pr, 2; ′Bu, 3) were produced upon treatment of complex 1 with ′PrN=C=N′Pr, ′PrNCO, or ′BuNCO. Reactions between complex 1 and CS2, ′BuNCS, or ′BuNCSe 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(n2-3-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) Å and Ti-O-P angle of 138.43(10)°. Estimates of Ti=O, Ti=S, Ti=Se, and Ti=NR bond strengths are discussed.

Original languageEnglish (US)
Pages (from-to)499-506
Number of pages8
JournalInorganic Chemistry
Volume40
Issue number3
DOIs
StatePublished - Jan 29 2001

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