二氮配位的高自旋二铁（I/II）物种。
Dinitrogen Coordination to a High-Spin Diiron(I/II) Species.
机构信息
Center for Catalysis and Florida Center for Heterocyclic Chemistry, Department of Chemistry, University of Florida, Gainesville, FL 32611, USA.
Department of Chemistry, Colorado State University, Fort Collins, CO 80523, USA.
出版信息
Angew Chem Int Ed Engl. 2022 May 23;61(22):e202202329. doi: 10.1002/anie.202202329. Epub 2022 Mar 31.
Dinitrogen coordination to iron centers underpins industrial and biological fixation in the Haber-Bosch process and by the FeM cofactors in the nitrogenase enzymes. The latter employ local high-spin metal centers; however, iron-dinitrogen coordination chemistry remains dominated by low-valent states, contrasting the enzyme systems. Here, we report a high-spin mixed-valent cis-(μ-1,2-dinitrogen)diiron(I/II) complex [(FeBr) (μ-N )L ] (2), where [L ] is a bis(β-diketiminate) cyclophane. Field-applied Mössbauer spectra, dc and ac magnetic susceptibility measurements, and computational methods support a delocalized S= / Fe N unit with D=-5.23 cm and consequent slow magnetic relaxation.
二氮配位铁中心是哈伯-博世工业固氮和固氮酶中铁钼辅因子的基础。后者利用局部高自旋金属中心；然而，铁-二氮配位化学仍然以低价态为主，与酶系统形成对比。在这里，我们报道了一个高自旋混合价顺式-（μ-1,2-二氮）二铁（I/II）配合物[(FeBr) (μ-N )L ]（2），其中[L ]是一个双（β-二酮亚胺）环戊烷。外磁场 Mössbauer 谱、直流和交流磁化率测量以及计算方法支持具有 S= / Fe N 单元的离域结构，D 值为-5.23 cm，导致缓慢的磁弛豫。
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