Ln4(CH2)4 Cubane-Type Rare-Earth Methylidene Complexes Consisting of "(C5Me4SiMe3)LnCH2" Units (Ln = Tm, Lu)

被引：74

作者：

Zhang, Wen-Xiong ^{[1
,2
,3
,4
]}

Wang, Zitao ^{[1
,2
,3
,4
]}

Nishiura, Masayoshi ^{[1
,2
]}

Xi, Zhenfeng ^{[3
,4
]}

Hou, Zhaomin ^{[1
,2
]}

机构：

[1] RIKEN, Adv Sci Inst, Organometall Chem Lab, Wako, Saitama 3510198, Japan

[2] RIKEN, Adv Sci Inst, Adv Catalyst Res Team, Wako, Saitama 3510198, Japan

[3] Peking Univ, Coll Chem, Minist Educ, BNLMS, Beijing 100871, Peoples R China

[4] Peking Univ, Coll Chem, Minist Educ, Key Lab Bioorgan Chem & Mol Engn, Beijing 100871, Peoples R China

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 15期

基金：

中国国家自然科学基金;

关键词：

C-H ACTIVATION; STRUCTURAL-CHARACTERIZATION; ALKYLIDENE COMPLEXES; METAL; CARBENE; REACTIVITY; EXISTENCE; POLYMERIZATION; CHEMISTRY; CATALYSTS;

D O I：

10.1021/ja200540b

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Tetranuclear cubane-type rare-earth methylidene complexes consisting of four "Cp'LnCH(2)" units, [Cp'Ln(mu(3)-CH2)](4) (4-Ln; Ln = Tm, Lu; Cp' = C5Me4SiMe3), have been obtained for the first time through CH4 elimination from the well-defined polymethyl complexes [Cp'Ln(mu(2)-CH3)(2)](3) (2-Ln) or mixed methyl/methylidene precursors such as [Cp'(3)Ln(3)(mu(2)-Me)(3)(mu(3)-Me)(mu(3)-CH2)] (3-Ln). The reaction of the methylidene complex 4-Lu with benzophenone leads to C=O bond cleavage and C=C bond formation to give the cubane-type oxo complex [Cp'Lu(mu(3)-O)](4) and CH2=CPh2, while the methyl/methylidene complex 3-Tm undergoes sequential methylidene addition to the C=O group and ortho C-H activation of the two phenyl groups of benzophenone to afford the bis(benzo-1,2-diyl)ethoxy-chelated trinuclear complex [Cp'Tm-3(3)(mu(2)-Me)(3){(C6H4)(2)C(O)Me}] (6-Tm).

引用

页码：5712 / 5715

页数：4

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