Reactivity of U3+ Metallocene Allyl Complexes Leads to a Nanometer-Sized Uranium Carbonate, [(C5Me5)2U]6(渭-魏1:魏2-CO3
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- 作者：Christopher L. Webster ; Joseph W. Ziller ; William J. Evans
- 刊名：Organometallics
- 出版年：2013
- 出版时间：September 9, 2013
- 年：2013
- 卷：32
- 期：17
- 页码：4820-4827
- 全文大小：456K
- 年卷期：v.32,no.17(September 9, 2013)
- ISSN：1520-6041
文摘
The U3+ allyl complexes (C5Me5)2U[CH2C(R)CH2] (R = H, Me) display three different types of reactivity, as exemplified by reactions with PhN鈺怤Ph, cyclooctatetraene, and CO2. Two equivalents of (C5Me5)2U[CH2C(R)CH2] effect a four-electron reduction of PhN鈺怤Ph to form the bis(imido) complex (C5Me5)2U(鈺怤Ph)2 and the bis(allyl) species (C5Me5)2U[CH2C(R)CH2]2. Two-electron reduction of C8H8 occurs to form (C5Me5)(C8H8)U[CH2C(R)CH2] products that contain only one cyclopentadienyl ring per metal. With CO2 at 80 psi, both reduction and insertion occur. A hexametallic uranium carbonate, [(C5Me5)2U]6(渭-魏1:魏2-CO3)6, is isolated as well as the bis(carboxylate) complexes (C5Me5)2U[魏2-O,O鈥?O2CCH2C(R)鈺怌H2]2. The polymetallic carbonate complex can also be synthesized from [(C5Me5)2U]2(渭-畏6:畏6-C6H6) and [(C5Me5)2U][(渭-Ph)2BPh2] and CO2.