Observation of Internal Electron Transfer in Bulky Allyl Ytterbium Complexes with Substituted Terpyridine Ligands
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- 作者：Rosemary E. White ; Christin N. Carlson ; Jacqueline M. Veauthier ; Cheslan K. Simpson ; J. D. Thompson ; Brian L. Scott ; Timothy P. Hanusa ; Kevin D. John
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：August 21, 2006
- 年：2006
- 卷：45
- 期：17
- 页码：7004 - 7009
- 全文大小：95K
- 年卷期：v.45,no.17(August 21, 2006)
- ISSN：1520-510X
文摘
A series of new bulky allyl terpyridyl-ytterbium complexes have been synthesized to determine the effect of allylligands on the internal charge-transfer process that exists in these materials. Compared to the pentamethylcyclopentadienyl-ytterbocene compound Cp*2Yb(tpyCN) (
C
N = 2172 cm-1), the symmetrically substituted allyl complex[1,3-(SiMe3)2C3H3]2Yb(tpyCN) possesses a markedly lowered CN frequency of 2130 cm-1. Furthermore, theelectronic nature of these bulky allyl complexes can be tuned, as demonstrated by the CN frequency of theasymmetric derivatives [1-(SiMe3)C3H4]2Yb(tpyCN) and [1-(SiPh3)-3-(SiMe3)C3H3]2Yb(tpyCN) (2171 and 2164 cm-1,respectively). The differences in these frequencies can be attributed to differences in the ligands' steric and electroniccharacter. Single-crystal X-ray characterization of [1,3-(SiMe3)2C3H3]2Yb(tpy) reveals that the allyl moiety possessesshorter Yb-C and Yb-N bond distances than the Cp* analogue. The magnetic susceptibility data for[1,3-(SiMe3)2C3H3]2Yb(tpy) departs dramatically from the Curie law, with a room-temperature magnetic moment of2.95 
B.
CN = 2172 cm-1), the symmetrically substituted allyl complex[1,3-(SiMe3)2C3H3]2Yb(tpyCN) possesses a markedly lowered CN frequency of 2130 cm-1. Furthermore, theelectronic nature of these bulky allyl complexes can be tuned, as demonstrated by the CN frequency of theasymmetric derivatives [1-(SiMe3)C3H4]2Yb(tpyCN) and [1-(SiPh3)-3-(SiMe3)C3H3]2Yb(tpyCN) (2171 and 2164 cm-1,respectively). The differences in these frequencies can be attributed to differences in the ligands' steric and electroniccharacter. Single-crystal X-ray characterization of [1,3-(SiMe3)2C3H3]2Yb(tpy) reveals that the allyl moiety possessesshorter Yb-C and Yb-N bond distances than the Cp* analogue. The magnetic susceptibility data for[1,3-(SiMe3)2C3H3]2Yb(tpy) departs dramatically from the Curie law, with a room-temperature magnetic moment of2.95 B.