Lutetium-Methanediide-Alkyl Complexes: Synthesis and Chemistry

	Lutetium-Methanediide-Alkyl Complexes: Synthesis and Chemistry
	Li, Shihui ; Wang, Meiyan ; Liu, Bo ; Li,Lei ; Cheng,Jianhua ; Wu,Chunji ; Liu,Dongtao ; Liu,Jingyao ; Cui,Dongmei
刊名	chemistry-a european journal
	2014
卷号	20 期号:47 页码:15493-15498
关键词	H BOND ACTIVATION METAL METHYLIDENE COMPLEXES RARE-EARTH STRUCTURAL-CHARACTERIZATION C-O METATHESIS REACTIONS CARBENE COMPLEXES IMIDO COMPLEXES YTTRIUM CARBENE CARBON-MONOXIDE
通讯作者	cui,dm
英文摘要	the first four-coordinate methanediide/alkyl lutetium complex (boddi) lu-2(ch2sime3)(2)(mu(2)-chsime3)(thf)(2) (boddi=arnc(me) chcochc(me) nar, ar=2,6-ipr(2)c(6)h(3)) (1) was synthesized by a thermolysis methodology through a-h abstraction from a lu-ch2sime3 group. complex 1 reacted with equimolar(2),6-iprc(6)h(3)nh(2) and ph2c=o to give the corresponding lutetium bridging imido and oxo complexes (boddi) lu-2(ch2sime3)(2)(mu(2)-n-2,6-ipr(2)c(6)h(3))(thf)(2) (2) and (boddi) lu-2(ch2sime3)(2)(mu(2)-o)(thf)(2) (3). treatment of 3 with ph2c=o (4 equiv) caused a rare insertion of lu-mu(2)-o bond into the c=o group to afford a diphenylmethyl diolate complex 4. reaction of 1 with phn=c=o (2 equiv) led to the migration of sime3 to the amido nitrogen atom to give complex (boddi) lu-2(ch2sime3)(2)-mu-{phnc(o)chc(o)nph(sime3)kappa n-3,o,o}(thf) (5). reaction of 1 with tbun equivalent to c formed an unprecedented product (boddi) lu-2(ch2sime3){mu(2)-[eta(2):eta(2)-tbunc(=ch2) sime2chc=ntbu-k 1n]}(tbun equivalent to c)(2) (6) through a cascade reaction of n equivalent to c bond insertion, sequential cyclometalative gamma-(sp(3))-h activation, c equivalent to c bond formation, and rearrangement of the newly formed carbene intermediate. the possible mechanistic pathways between 1, phn=c=o, and tbun equivalent to c were elucidated by dft calculations.
收录类别	SCI
语种	英语
WOS记录号	WOS:000345234800030
内容类型	期刊论文
源URL	[http://ir.ciac.jl.cn/handle/322003/52409]
专题	长春应用化学研究所_长春应用化学研究所知识产出_期刊论文
推荐引用方式 GB/T 7714	Li, Shihui,Wang, Meiyan,Liu, Bo,et al. Lutetium-Methanediide-Alkyl Complexes: Synthesis and Chemistry[J]. chemistry-a european journal,2014,20(47):15493-15498.
APA	Li, Shihui.,Wang, Meiyan.,Liu, Bo.,Li,Lei.,Cheng,Jianhua.,...&Cui,Dongmei.(2014).Lutetium-Methanediide-Alkyl Complexes: Synthesis and Chemistry.chemistry-a european journal,20(47),15493-15498.
MLA	Li, Shihui,et al."Lutetium-Methanediide-Alkyl Complexes: Synthesis and Chemistry".chemistry-a european journal 20.47(2014):15493-15498.