Doyle Laurence R, Scott Daniel J, Hill Peter J, Fraser Duncan A X, Myers William K, White Andrew J P, Green Jennifer C, Ashley Andrew E
Department of Chemistry , Imperial College London , London SW7 2AZ , UK . Email:
Inorganic Chemistry Laboratory , University of Oxford , Oxford OX1 3QR , UK.
Chem Sci. 2018 Jul 18;9(37):7362-7369. doi: 10.1039/c8sc01841c. eCollection 2018 Oct 7.
The synthesis and characterisation of the = 1/2 Fe(i) complex [Fe(depe)][BArF4] ([][BArF4]), and the facile reversible binding of N and H in both solution and the solid state to form the adducts [·N] and [·H], are reported. Coordination of N in THF is thermodynamically favourable under ambient conditions (1 atm; Δ = -4.9(1) kcal mol), while heterogenous binding is more favourable for H than N by a factor of ∼300. [·H][BArF4] represents a rare example of a well-defined, open-shell, non-classical dihydrogen complex, as corroborated by ESR spectroscopy. The rapid exchange between N and H coordination under ambient conditions is unique for a paramagnetic Fe complex.
报道了自旋量子数S = 1/2的铁(I)配合物[Fe(depe)][BArF4]([ ][BArF4])的合成与表征,以及在溶液和固态中N和H的易逆结合形成加合物[·N]和[·H]。在环境条件(1个大气压;ΔG = -4.9(1) kcal mol)下,N在四氢呋喃中的配位在热力学上是有利的,而异质结合对H比对N更有利,约为300倍。[·H][BArF4]代表了一个明确的、开壳层的、非经典二氢配合物的罕见例子,这一点得到了电子顺磁共振光谱的证实。在环境条件下,N和H配位之间的快速交换对于顺磁性铁配合物来说是独一无二的。