Mullane Kimberly C, Ryu Ho, Cheisson Thibault, Grant Lauren N, Park Ji Young, Manor Brian C, Carroll Patrick J, Baik Mu-Hyun, Mindiola Daniel J, Schelter Eric J
Department of Chemistry , University of Pennsylvania , 231 South 34th Street , Philadelphia Pennsylvania 19104 , United States.
Department of Chemistry , Korea Advanced Institute of Science and Technology (KAIST) , Daejeon 34141 , Republic of Korea.
J Am Chem Soc. 2018 Sep 12;140(36):11335-11340. doi: 10.1021/jacs.8b06090. Epub 2018 Aug 30.
Uranium complexes in the +3 and +4 oxidation states were prepared using the anionic PN (PN = ( N-(2-(diisopropylphosphino)-4-methylphenyl)-2,4,6-trimethylanilide) ligand framework. New complexes include the halide starting materials, (PN)UI (1) and (PN)UCl (2), which both yield (PN)U(N) (3) by reaction with NaN. Compound 3 was reduced with potassium graphite to produce a putative, transient uranium-nitrido moiety that underwent an intramolecular C-H activation to form a rare example of a parent imido complex, [K(THF)][(PN)U(═NH)[ PrP(CHMe)N(CHMeCH)]] (4). Calculated reaction energy profiles strongly suggest that a C-H insertion becomes unfavorable when a reductant is present, offering a distinctively different reaction pathway than previously observed for other uranium nitride complexes.
使用阴离子型PN（PN =（N-（2-（二异丙基膦基）-4-甲基苯基）-2,4,6-三甲基苯胺）配体框架制备了氧化态为+3和+4的铀配合物。新的配合物包括卤化物起始原料（PN）UI（1）和（PN）UCl（2），它们与NaN反应均生成（PN）U（N）（3）。化合物3用石墨钾还原，生成一个假定的瞬态铀氮化物部分，该部分经历分子内C-H活化，形成了一个罕见的母体亚胺基配合物实例，即[K（THF）][（PN）U（═NH）[PrP（CHMe）N（CHMeCH）]]（4）。计算得到的反应能量曲线强烈表明，当存在还原剂时，C-H插入变得不利，这提供了一条与其他铀氮化物配合物以前观察到的明显不同的反应途径。
