A Mononuclear Iron Thiolate Complex with N-Heterocyclic Carbene Ligation
Received date: 2022-01-21
Online published: 2022-02-15
Supported by
National Natural Science Foundation of China(21725104); National Natural Science Foundation of China(22061160464); National Natural Science Foundation of China(21821002); Program of Shanghai Academic Research Leader(19XD1424800); K. C. Wong Education Foundation
The relevance of low-valent iron complexes bearing sulfur-containing ligands with the reactive iron intermediates in enzymatic dinitrogen fixation has stimulated great synthetic efforts toward them. Low-valent iron thiolate complexes have been mostly known for the thiolate-bridged diiron(I) carbonyl compounds. In contrast, isolable mononuclear iron(I) thiolate complexes are exceedingly rare. Herein, we report the synthesis and characterization of a mononuclear iron(I) complex [(IMes)Fe(SAr*)] (1, IMes=1,3-bis(mesityl)imidazole-2-ylidene, Ar*=2,6-(2',4',6'-Pri3C6H2)2C6H3) as well as its catalytic performance in dinitrogen silylation reaction. Complex 1 was synthesized from the reaction of (IMes)2FeBr with KSAr* in Et2O in 81% isolated yield. Single-crystal X-ray diffraction studies revealed that the thiolate ligand in 1 is coordinating to the iron center in an σ:η6-fashion via the sulfur atom and one of the flanking Pri3C6H2 ring with the Fe—S distance of 0.2228(1) nm and the Fe—C(Trip) distances ranging from 0.2076(2) to 0.2205(2) nm. Zero-field 57Fe Mössbauer spectrum at 80 K (δ=0.56 mm•s-1; ΔEQ=0.98 mm•s-1) and X-band electron paramagnetic resonance data (g=[2.20, 2.03, 1.99]) at 103 K of 1 point to its low-spin iron(I) nature (S=1/2). These data are comparable with those of Holland's iron(I) thiolate complex K[(2-S-1,3-(6-F-3-(2,4,6-Pri3C6H2)C6H2)2C6H4)Fe] (Nature 2015, 526, 96). Density functional theory studies support the S=1/2 ground spin-state for 1 and reveal that the interaction between the iron atom and the sulfur atom is essentially σ-bonding in character. In addition, π- and δ-type interactions between the iron atom and the η6-Pri3C6H2 ring in 1 also exist. Complex 1 can catalyze the reaction of N2 with KC8 and Me3SiCl in Et2O at room temperature, affording N(SiMe3)3 with a turn-over number up to 73 in 24 h and 87 in 48 h. The reaction employing (IMes)2FeBr as catalyst has a turn-over number up to 73 in 24 h and elongating the reaction time to 48 h does not lead to further increase of the turn-over number. The fine catalytic performance with 1 over (IMes)2FeBr implies that the thiolate ligand in 1 might render the catalytically active intermediate a relatively long lifetime.
Key words： N-heterocyclic carbene; iron; sulfur ligand; N2 activation; low valent
Shangzhao Li , Zhenwu Ouyang , Junjie Zou , Dongyang Wang , Bin Xu , Liang Deng . A Mononuclear Iron Thiolate Complex with N-Heterocyclic Carbene Ligation[J]. Acta Chimica Sinica, 2022 , 80(3) : 272 -276 . DOI: 10.6023/A22010038
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