Four- and Five-Coordinate Osmium(IV) Nitrides and Imides: Circumventing the “Nitrido Wall”
作者:Josh Abbenseth、Sarah C. Bete、Markus Finger、Christian Volkmann、Christian Würtele、Sven Schneider
DOI:10.1021/acs.organomet.7b00707
日期:2018.3.12
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 [OsIVN(PNP)] (PNP = N(CHCHPtBu2)2). From there, a square-pyramidal isonitrile adduct could
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。