Application of a New Versatile Ligand to Lanthanide(II) Chemistry: Synthesis, Reactivity, and Structure of a New Class of Organolanthanide Complexes
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- 作者：Zuowei Xie ; Shaowu Wang ; Qingchuan Yang ; and Thomas C. W. Mak
- 刊名：Organometallics
- 出版年：1999
- 出版时间：June 21, 1999
- 年：1999
- 卷：18
- 期：13
- 页码：2420 - 2427
- 全文大小：141K
- 年卷期：v.18,no.13(June 21, 1999)
- ISSN：1520-6041
文摘
Reaction of Me2Si(C9H7)Cl with 1 equiv of Li2C2B10H10 gave, after hydrolysis, the newversatile ligand Me2Si(C9H7)(C2B10H11) (1). 1 can be conveniently converted into themonoanion [Me2Si(C9H6)(C2B10H11)]- (2) and the dianion [Me2Si(C9H6)(C2B10H10)]2- (3) bytreatment with 1 equiv or excess amounts of NaH, respectively. Treatment of SmI2 with 2in THF gave the unexpected redox product [
5:6-Me2Si(C9H6)(C2B10H11)]Sm(THF)2 (4).Reaction of SmI2 with 1 equiv of 3 in THF, followed by reaction with 2, gave the unexpectedC-H bond reduction product [{5:
-Me2Si(C9H6)(C2B10H10)}2Sm][Na(THF)6] (5). In contrast,reaction of YbI2 with 1 or 2 equiv of 2 afforded [{5-Me2Si(C9H6)(C2B10H11)}Yb(
-I)(THF)2]2(6) or [5-Me2Si(C9H6)(C2B10H11)]2Yb(THF)2 (7), respectively. Treatment of YbI2 with 1 equivof 3 in THF gave [5:-Me2Si(C9H6)(C2B10H10)]Yb(THF)3 (8), which is the first mixed-ligandorganolanthanide(II) complex containing both Ln-C 
and bonds to be reported. 8 canalso be prepared from the reaction of 6 with excess NaH in THF. Reaction of 8 with 1 equivof 2 in THF yielded [5-Me2Si(C9H6)(C2B10H11)]Yb(THF)[(-5):-Me2Si(C9H6)(C2B10H10)]Na(THF)3 (9), which can also be prepared by reaction of 7 with 1 equiv of NaH in THF. Thesenew complexes have been fully characterized by 1H, 13C, and 11B NMR, IR spectroscopy,and elemental analyses. The molecular structures of 4, 5, 8, and 9 have been furtherconfirmed by single-crystal X-ray analyses.
5:6-Me2Si(C9H6)(C2B10H11)]Sm(THF)2 (4).Reaction of SmI2 with 1 equiv of 3 in THF, followed by reaction with 2, gave the unexpectedC-H bond reduction product [{5:-Me2Si(C9H6)(C2B10H10)}2Sm][Na(THF)6] (5). In contrast,reaction of YbI2 with 1 or 2 equiv of 2 afforded [{5-Me2Si(C9H6)(C2B10H11)}Yb(-I)(THF)2]2(6) or [5-Me2Si(C9H6)(C2B10H11)]2Yb(THF)2 (7), respectively. Treatment of YbI2 with 1 equivof 3 in THF gave [5:-Me2Si(C9H6)(C2B10H10)]Yb(THF)3 (8), which is the first mixed-ligandorganolanthanide(II) complex containing both Ln-C and bonds to be reported. 8 canalso be prepared from the reaction of 6 with excess NaH in THF. Reaction of 8 with 1 equivof 2 in THF yielded [5-Me2Si(C9H6)(C2B10H11)]Yb(THF)[(-5):-Me2Si(C9H6)(C2B10H10)]Na(THF)3 (9), which can also be prepared by reaction of 7 with 1 equiv of NaH in THF. Thesenew complexes have been fully characterized by 1H, 13C, and 11B NMR, IR spectroscopy,and elemental analyses. The molecular structures of 4, 5, 8, and 9 have been furtherconfirmed by single-crystal X-ray analyses.