Selectivity in the Self-Assembly of Organometallic Gold(I) Rings and [2]Catenanes
详细信息 查看全文
- 作者：Nicolle C. Habermehl ; Michael C. Jennings ; Christopher P. McArdle ; Fabian Mohr ; and Richard J. Puddephatt
- 刊名：Organometallics
- 出版年：2005
- 出版时间：October 10, 2005
- 年：2005
- 卷：24
- 期：21
- 页码：5004 - 5014
- 全文大小：338K
- 年卷期：v.24,no.21(October 10, 2005)
- ISSN：1520-6041
文摘
The selectivity of formation of organometallic rings or [2]catenanes [{X(4-C6H4OCH2C
CAu)2(
-Ph2PZPPh2)}n], n =1 or 2, respectively, has been studied as a function of thehinge group X and the diphosphine ligand [X = O, S, SO2, CH2, CMe2, CPh2, C(CF3)2, C6H10;Z = (CH2)m with m = 2-5]. When Z = (CH2)3, mixing of pairs of compounds with differentC2v-symmetrical hinge groups (X, X' = SO2, CH2, CMe2, CPh2, C(CF3)2, C6H10) led to formationof an equilibrium mixture containing the unsymmetrical [2]catenanes [{X(4-C6H4OCH2CCAu)2(-Ph2PZPPh2)}{X'(4-C6H4OCH2CCAu)2(-Ph2PZPPh2)], as identified by NMRspectroscopy. The complexes with Z = (CH2)4 exist in solution predominantly as themacrocycles and so do not form analogous mixed diacetylide complexes. When the hingegroup contained a prochiral carbon center (X = CHMe, CMePh, 1,1-indanylidene), only achiralmacrocycles [X(4-C6H4OCH2CCAu)2(-Ph2PZPPh2)] were formed in solution when Z =(CH2)4, but mixtures containing both achiral macrocycles and chiral [2]catenane were formedwhen Z = (CH2)3. In several cases, the solid-state structures of the isolated complexes werenot representative of the structures in solution, with macrocycles being dominant in solutionand [2]catenanes formed preferentially during crystallization.
CAu)2(-Ph2PZPPh2)}n], n =1 or 2, respectively, has been studied as a function of thehinge group X and the diphosphine ligand [X = O, S, SO2, CH2, CMe2, CPh2, C(CF3)2, C6H10;Z = (CH2)m with m = 2-5]. When Z = (CH2)3, mixing of pairs of compounds with differentC2v-symmetrical hinge groups (X, X' = SO2, CH2, CMe2, CPh2, C(CF3)2, C6H10) led to formationof an equilibrium mixture containing the unsymmetrical [2]catenanes [{X(4-C6H4OCH2CCAu)2(-Ph2PZPPh2)}{X'(4-C6H4OCH2CCAu)2(-Ph2PZPPh2)], as identified by NMRspectroscopy. The complexes with Z = (CH2)4 exist in solution predominantly as themacrocycles and so do not form analogous mixed diacetylide complexes. When the hingegroup contained a prochiral carbon center (X = CHMe, CMePh, 1,1-indanylidene), only achiralmacrocycles [X(4-C6H4OCH2CCAu)2(-Ph2PZPPh2)] were formed in solution when Z =(CH2)4, but mixtures containing both achiral macrocycles and chiral [2]catenane were formedwhen Z = (CH2)3. In several cases, the solid-state structures of the isolated complexes werenot representative of the structures in solution, with macrocycles being dominant in solutionand [2]catenanes formed preferentially during crystallization.© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |