Hydrogenolysis and Protonation of Polymetallic Lutetium Methylidene and Methyl Complexes
详细信息 查看全文
- 作者：Tingting Li ; Masayoshi Nishiura ; Jianhua Cheng ; Wenxiong Zhang ; Yang Li ; Zhaomin Hou
- 刊名：Organometallics
- 出版年：2013
- 出版时间：August 12, 2013
- 年：2013
- 卷：32
- 期：15
- 页码：4142-4148
- 全文大小：329K
- 年卷期：v.32,no.15(August 12, 2013)
- ISSN：1520-6041
文摘
We report the hydrogenolysis and protonation reactions of a tetrametallic lutetium tetramethylidene complex [Cp鈥睱u(渭3-CH2)]4 (Cp鈥?= C5Me4SiMe3) (1) and a trimetallic lutetium hexamethyl complex [Cp鈥睱u(渭2-CH3)2]3 (2) with H2 and ammonium borate compounds. The hydrogenolysis of 1 with H2 afforded the corresponding tetrahydride tetramethyl complex [Cp鈥?sub>4Lu4(渭4-H)(渭3-H)(渭2-H)2(渭2-Me)4] (3) in 87% yield. In this transformation, each of the four [Lu-渭2-CH2] methylidene groups in 1 reacted with one molecule of H2 to give a mixed methyl/hydride 鈥淟u(H)CH3鈥?unit. The reaction of 1 with [PhMe2NH][B(C6F5)4] gave the cationic tetrametallic lutetium monomethyl trimethylidene complex [Cp鈥?sub>4Lu4(渭3-CH2)3(渭3-CH3)][B(C6F5)4] (4) in 85% yield, through protonation of one of the four methylidene units in 1 with the anilinium borate. In contrast, the reaction of the trimetallic hexamethyl complex 2 with H2 led to formation of a tetrametallic lutetium monohydride heptamethyl complex [Cp鈥?sub>4Lu4(渭4-H)(渭3-Me)(渭2-Me)6] (5) in 65% yield, while the protonation reaction of 2 with 3 equiv of [Et3NH][BPh4] gave a monometallic lutetium monomethyl contact-ion-pair complex [Cp鈥睱uMe(畏6-Ph)(畏1-Ph)BPh2] (6) in 81% yield. Complexes 3鈥?b>6 were fully characterized by 1H and 13C NMR, single-crystal X-ray diffraction, and micro elemental analyses.