Four- and Five-Coordinate Osmium(IV) Nitrides and Imides: Circumventing the “Nitrido Wall”,Organometallics

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Four- and Five-Coordinate Osmium(IV) Nitrides and Imides: Circumventing the “Nitrido Wall”
Organometallics ( IF 2.5 ) Pub Date : 2017-10-31 00:00:00 , DOI: 10.1021/acs.organomet.7b00707
Josh Abbenseth ₁ , Sarah C. Bete ₁ , Markus Finger ₁ , Christian Volkmann ₁ , Christian Würtele ₁ , Sven Schneider ₁

Affiliation

Osmium nitride chemistry is dominated by osmium(VI) in octahedral or square-pyramidal coordination. The stability of the d² configuration and preference of the strong σ- and π-donor nitride for apical coordination is in line with the Gray–Ballhausen bonding model. In contrast, low-valent osmium(IV) or other d⁴ nitrides are rare and have only been reported with lower coordination numbers (CN ≤ 4), thereby avoiding π-bonding conflicts of the nitride ligand with the electron-rich metal center. We here report the synthesis of the square-planar osmium(IV) nitride [Os^IVN(PNP)] (PNP = N(CHCHPtBu₂)₂). From there, a square-pyramidal isonitrile adduct could be isolated, which surprisingly features basal nitride coordination. Analysis of this five-coordinate d⁴ nitride shows an unusual binding mode of the isonitrile ligand, which explains the preference of the weakest σ-donor and strongest π-acceptor isonitrile for apical coordination.

中文翻译：

四坐标和五坐标Ni（IV）氮化物和酰亚胺：绕过“ Nitrido墙”

氮化（化学在八面体或方金字塔形配位中以by（VI）为主。d ²构型的稳定性以及强烈的σ-和π-给体氮化物对顶端配位的偏爱与Gray-Ballhausen键合模型一致。相比之下，低价IV（IV）或其他d ⁴氮化物很少见，而且据报道仅具有较低的配位数（CN≤4），从而避免了氮化物配体与富电子金属中心的π键冲突。我们在这里报告了方形氮化nitride [Os ^IV N（PNP）]（PNP = N（CHCHP t Bu ₂）₂）的合成）。从那里，可以分离出一个方形-金字塔形的异腈加合物，其具有令人惊讶的基氮化物配位的特征。分析这种五坐标的d ⁴氮化物显示出异腈配体的不寻常结合方式，这说明了最弱的σ供体和最强的π受体异腈对根尖配位的偏爱。

更新日期：2018-02-02

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