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首页> 外文期刊>Chemistry: A European journal >Synthesis and insertion chemistry of mixed tether uranium metallocene complexes
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Synthesis and insertion chemistry of mixed tether uranium metallocene complexes

机译：混合系绳铀茂金属配合物的合成和插入化学

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摘要

The synthesis of mixed tethered alkyl uranium metallocenes has been investigated by examining the reactivity of the bis(tethered alkyl) metallocene [(η~5-C_5Me_4SiMe_2CH_2-IκC)_2U] (1) with substrates that react with only one of the U-C linkages. The effect of these mixed tether coordination environments on the reactivity of the remaining U-C bond has been studied by using CO insertion chemistry. One equivalent of azidoadamantane (AdN_3) reacts with 1 to yield the mixed tethered alkyl triazenido complex [(η~5-C_5Me_4SiMe_2CH_2-IκC)U(η~5-C_5Me_4SiMe_2-CH 2NNN-Ad-Iκ~2N~(1,3))]. Similarly, a single equivalent of CS_2 reacts with 1 to form the mixed tethered alkyl dithiocarboxylate complex [(η~5-C_5Me_4SiMe_2CH_2-IκC) U(η~5-C_5Me_4SiMe_2- CH_2C(S)_2-Iκ~2S,S')], a reaction that constitutes the first example of CS_2 insertion into a U~(4+)-C bond. Complex 1 reacts with one equivalent of pyridine N-oxide by C-H bond activation of the pyridine ring to form a mixed tethered alkyl cyclometalated pyridine N-oxide complex [(η~5-C_5Me_4SiMe_2CH_2-IκC)(η~5-C_5Me_4SiMe_3)U(C_6H_4NO- Iκ~2C,O)]. The remaining (η~5-C_5Me_4SiMe_2CH_2-IκC)~2- ligand in each of these mixed tethered species show reactivity towards CO and tethered enolate ligands form by insertion. Subsequent rearrangement have been identified in [(η~5-C_5Me_4SiMe_3)U(C_5H_4NO-Iκ~2C,O)(η~5-C_5Me_4SiMe_2C(=CH_2)O-IκO)] and [(η~5-C_5Me_4SiMe_2CH_2NNN-Ad-Iκ~2N~(1,3))U(η~5- C_5Me_4SiMe_2C(=CH_2)O-IκO)].
机译：通过检查双（拴系烷基）金属茂[[η〜5-C_5Me_4SiMe_2CH_2-IκC）_2U]（1）与仅与U-C键之一反应的底物的反应性，研究了混合拴系烷基铀茂金属的合成。已经通过使用CO插入化学研究了这些混合的系链配位环境对剩余的U-C键的反应性的影响。一当量的叠氮金刚烷（AdN_3）与1反应生成混合的链状烷基三氮杂ido络合物[（η〜5-C_5Me_4SiMe_2CH_2-IκC）U（η〜5-C_5Me_4SiMe_2-CH2NNN-Ad-Iκ〜2N〜（1,3） ）]。类似地，单当量的CS_2与1反应形成混合的束缚烷基二硫代羧酸酯络合物[（η〜5-C_5Me_4SiMe_2CH_2-IκC）U（η〜5-C_5Me_4SiMe_2- CH_2C（S）_2-Iκ〜2S，S']] ，是构成CS_2插入U〜（4 +）-C键的第一个例子的反应。配合物1通过吡啶环的CH键活化与一当量的吡啶N-氧化物反应形成混合的束缚烷基环金属化吡啶N-氧化物配合物[[η〜5-C_5Me_4SiMe_2CH_2-IκC）（η〜5-C_5Me_4SiMe_3）U（ C_6H_4NO-Iκ〜2C，O）]。这些混合的束缚物种中的每一个中剩余的（η〜5-C_5Me_4SiMe_2CH_2-IκC）〜2-配体表现出对CO的反应性，并且通过插入形成了束缚的烯酸酯配体。在[[η〜5-C_5Me_4SiMe_3）U（C_5H_4NO-Iκ〜2C，O）（η〜5-C_5Me_4SiMe_2C（= CH_2）O-IκO）]和[[η〜5-C_5Me_4SiMe_2CH_2NNN-Ad- Iκ〜2N〜（1,3））U（η〜5- C_5Me_4SiMe_2C（= CH_2）O-IκO）]。

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