（TTP）Ti（η2-3-己炔）的原子转移反应：反式-（TTP）Ti[OP（Oct）3]2的合成与分子结构

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

作者信息

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

机构信息

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

出版信息

Inorg Chem. 2001 Jan 29;40(3):499-506. doi: 10.1021/ic0003426.

DOI:10.1021/ic0003426

PMID:11209607

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.

摘要

人们发现，杂累积烯与(TTP)Ti(η²-3-己炔)1（TTP = 内消旋-5,10,15,20-四对甲苯基卟啉二价阴离子）之间会发生原子和基团转移反应。用异丙基异氰酸酯、异丙基异氰酸酯或叔丁基异氰酸酯处理配合物1时，会生成亚氨基衍生物(TTP)Ti=NR（R = 异丙基，2；叔丁基，3）。配合物1与二硫化碳、叔丁基异硫氰酸酯或叔丁基异硒氰酸酯之间的反应得到了硫族化物配合物(TTP)Ti=Ch（Ch = 硒，4；硫，5）。用2当量的三乙基膦处理配合物1得到双(膦)配合物(TTP)Ti(PEt₃)₂，6。尽管(TTP)Ti(η²-3-己炔)很容易从环氧化物和亚砜中夺取氧，但1与三辛基氧化膦之间的反应并未导致氧原子转移。相反，形成了顺磁性的钛(II)衍生物(TTP)Ti[O=P(Oct)₃]₂，7。通过单晶X射线衍射确定了配合物7的分子结构：Ti-O距离为2.080(2) Å，Ti-O-P角度为138.43(10)°。讨论了Ti=O、Ti=S、Ti=Se和Ti=NR键强度的估计值。