Reactivity of U3+ Metallocene Allyl Complexes Leads to a Nanometer-Sized Uranium Carbonate, [(C5Me5)2U]6(μ-κ1:κ2-CO3)6

被引:17
作者
Webster, Christopher L. [1 ]
Ziller, Joseph W. [1 ]
Evans, William J. [1 ]
机构
[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA
关键词
SMALL-MOLECULE ACTIVATION; INSERTION CHEMISTRY; DIOXIDE; OXO; CO2; DINITROGEN; REDUCTION; VALENT; MONOXIDE; LIGANDS;
D O I
10.1021/om400526h
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The U3+ allyl complexes (C5Me5)(2)U[CH2C(R)CH2] (R = H, Me) display three different types of reactivity, as exemplified by reactions with PhN=NPh, cyclooctatetraene, and CO2. Two equivalents of (C5Me5)(2)U[CH2C(R)CH2] effect a four-electron reduction of PhN=NPh to form the bis(imido) complex (C5Me5)(2)U(=NPh)(2) and the bis(allyl) species (C5Me5)(2)U[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)(2)U](6)(mu-kappa(1):kappa(2)-CO3)(6), is isolated as well as the bis(carboxylate) complexes (C5Me5)(2)U[kappa(2)-O,O'-O2CCH2C(R)=CH2](2). The polymetallic carbonate complex can also be synthesized from [(C5Me5)(2)U](2)(mu-eta(6):eta(6)-C6H6) and [(C5Me5)(2)U][(mu-Ph)(2)BPh2] and CO2.
引用
收藏
页码:4820 / 4827
页数:8
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