Catalytic Nitrogen-to-Ammonia Conversion by Osmium and Ruthenium Complexes.
Catalytic Nitrogen-to-Ammonia Conversion by Osmium and Ruthenium Complexes.
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DOI：
10.1021/jacs.7b10204
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发表时间：
2017-11-15
影响因子：
15
通讯作者：
Peters JC
中科院分区：
文献类型：
--
作者：
Fajardo J Jr;Peters JC
尽管钌和锇络合物在过渡金属二氮化学的发展中发挥了关键作用，但它们以前没有显示出介导催化N2至NH3转化（N2 RR），也没有M-NxHy络合物衍生自M-N2前体的质子化（M = Ru，Os）。为了帮助划定N2 RR催化的关键因素，我们报告的同构三（膦基）甲硅烷基钌和锇络合物介导催化N2 RR，并比较其活动与同构铁络合物。Os系统是最活跃的，并且被证明在使用Cp*2Co和[H2 NPh 2][OTf]作为还原剂和酸源的单批实验中每个Os中心释放超过120当量的NH3。在相同条件下，同构Ru和Fe络合物产生非常少的NH3。Os-N2-阴离子态的质子化提供了结构特征为Os= NNH 2+肼基的物种，其本身介导NH3的产生，表明它是催化的可能中间体。Os-氢化物物种的特征在于在催化过程中作为非活性物种形成。
Despite the critical role ruthenium and osmium complexes have played in the development of transition metal dinitrogen chemistry, they have not been previously shown to mediate catalytic N2-to-NH3 conversion (N2RR), nor have M-NxHy complexes been derived from protonation of M-N2 precursors (M = Ru, Os). To help delineate key factors for N2RR catalysis, we report on isostructural tris(phosphino)silyl Ru and Os complexes that mediate catalytic N2RR, and compare their activities with an isostructural iron complex. The Os system is most active, and is demonstrated to liberate more than 120 equiv NH3 per Os center in a single batch experiment using Cp*2Co and [H2NPh2][OTf] as the reductant and acid source. Isostructural Ru and Fe complexes generate very little NH3 under the same conditions. Protonation of an anionic Os-N2− state affords a structurally characterized Os=NNH2+ hydrazido species that itself mediates NH3 generation, suggesting it is a plausible intermediate of the catalysis. Os-hydride species are characterized that form during catalysis as inactive species.
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影响因子：
4.6
作者：
BUHR, JD;TAUBE, H
通讯作者：
TAUBE, H
DOI：
10.1039/c39890001883
发表时间：
1989-12-15
影响因子：
--
作者：
CHE, CM;LAM, HW;LAU, TC
通讯作者：
LAU, TC
影响因子：
15
作者：
COLLMAN, JP;ROPER, WR
通讯作者：
ROPER, WR
影响因子：
16.6
作者：
Eizawa A;Arashiba K;Tanaka H;Kuriyama S;Matsuo Y;Nakajima K;Yoshizawa K;Nishibayashi Y
通讯作者：
Nishibayashi Y
DOI：
10.1002/anie.201703244
发表时间：
2017-06-06
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Buscagan TM;Oyala PH;Peters JC
通讯作者：
Peters JC