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

来源：

ORGANOMETALLICS | 2013年 / 32卷 / 17期

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

页码：4820 / 4827

页数：8

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