Dau Phuong D, Vasiliu Monica, Peterson Kirk A, Dixon David A, Gibson John K
Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California, 94720, USA.
Department of Chemistry, The University of Alabama, Shelby Hall, Tuscaloosa, Alabama, 35487-0336, USA.
Chemistry. 2017 Dec 6;23(68):17369-17378. doi: 10.1002/chem.201704193. Epub 2017 Nov 10.
Actinyl chemistry is extended beyond Cm to BkO and CfO through transfer of an O atom from NO to BkO or CfO , establishing a surprisingly high lower limit of 73 kcal mol for the dissociation energies, D[O-(BkO )] and D[O-(CfO )]. CCSD(T) computations are in accord with the observed reactions, and characterize the newly observed dioxide ions as linear pentavalent actinyls; these being the first Bk and Cf species with oxidation states above IV. Computations of actinide dioxide cations AnO for An=Pa to Lr reveal an unexpected minimum for D[O-(CmO )]. For CmO , and AnO beyond EsO , the most stable structure has side-on bonded η -(O ), as An peroxides for An=Cm and Lr, and as An superoxides for An=Fm, Md, and No. It is predicted that the most stable structure of EsO is linear [O=Es =O] , einsteinyl, and that FmO and MdO , like CmO , also have actinyl(V) structures as local energy minima. The results expand actinide oxidation state chemistry, the realm of the distinctive actinyl moiety, and the non-periodic character towards the end of the periodic table.
通过将一个氧原子从一氧化氮转移到锫酰（BkO）或锎酰（CfO），锕系元素酰基化学从锔（Cm）扩展到了锫酰（BkO）和锎酰（CfO），确定了离解能D[O-(BkO)]和D[O-(CfO)]令人惊讶的73千卡·摩尔的高下限。耦合簇单双激发组态相互作用并包含微扰三重激发（CCSD(T)）计算结果与观察到的反应一致，并将新观察到的二氧化物离子表征为线性五价锕系元素酰基；这些是氧化态高于IV的首个锫和锎物种。对锕系元素二氧化物阳离子AnO（An = 镤（Pa）到铹（Lr））的计算揭示了D[O-(CmO)]的意外最小值。对于CmO以及EsO之后的AnO，最稳定的结构具有侧基键合的η -(O)，对于An = Cm和Lr为An过氧化物，对于An = Fm、Md和No为An超氧化物。据预测，EsO最稳定的结构是线性的[O=Es =O]，即锿酰，并且FmO和MdO，与CmO一样，也具有作为局部能量最小值的酰基(V)结构。这些结果扩展了锕系元素氧化态化学、独特的锕系元素酰基部分的范围以及元素周期表末尾的非周期性特征。
