TY - JOUR
T1 - Atom transfer reactions of (TTP)Ti(n2-3-hexyne)
T2 - Synthesis and molecular structure of trans-(TTP)Ti[OP(Oct)3]2
AU - Thorman, J. L.
AU - Young, V. G.
AU - Boyd, P. D.W.
AU - Guzei, I. A.
AU - Woo, L. K.
PY - 2001/1/29
Y1 - 2001/1/29
N2 - 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.
AB - 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.
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U2 - 10.1021/ic0003426
DO - 10.1021/ic0003426
M3 - Article
C2 - 11209607
AN - SCOPUS:0035966710
SN - 0020-1669
VL - 40
SP - 499
EP - 506
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 3
ER -