Heterometallic Homo- and Heteroleptic Porphyrinate Dimers with a Rhodium-Thallium Bond
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- 作者：Dimitra Daphnomili ; W. Robert Scheidt ; Jaroslav Zajicek ; and Athanassios G. Coutsolelos
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：July 27, 1998
- 年：1998
- 卷：37
- 期：15
- 页码：3675 - 3681
- 全文大小：112K
- 年卷期：v.37,no.15(July 27, 1998)
- ISSN：1520-510X
文摘
The synthesis and spectroscopic characterization of four heterometallic porphyrinate dimers containing rhodium-thallium metal-metal bonds are reported. The investigated compounds are represented by the formula (Porph)Rh-Tl(Porph'), where Porph and Porph' are OEP and/or TPP. UV/visible spectroscopy of the title complexesconfirms the presence of a strong 
- interaction between the macrocycles in each derivative. With 1H and 13CNMR data, we were able to distinguish two major NMR regions: the endo, between the metal-metal bondedmacrocycles, and the exo, outside the macrocycles, which are characteristic features of porphyrinic dimers. 205TlNMR for the title complexes was performed, and the chemical shifts of the thallium nucleus are presented. Forthe four complexes, the magnitudes of spin-spin coupling constants between thallium and rhodium nuclei havebeen measured for the first time. Finally, reactions with selected substrates were studied in order to investigatethe reactivity as well as the polarity of the metal-metal bond.
- interaction between the macrocycles in each derivative. With 1H and 13CNMR data, we were able to distinguish two major NMR regions: the endo, between the metal-metal bondedmacrocycles, and the exo, outside the macrocycles, which are characteristic features of porphyrinic dimers. 205TlNMR for the title complexes was performed, and the chemical shifts of the thallium nucleus are presented. Forthe four complexes, the magnitudes of spin-spin coupling constants between thallium and rhodium nuclei havebeen measured for the first time. Finally, reactions with selected substrates were studied in order to investigatethe reactivity as well as the polarity of the metal-metal bond.