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| Synthesis and bonding analysis of low-coordinate Fe and Cr complexes with ultra-bulky silylamino groups |
| Author Name | Affiliation | E-mail | | ZHENG Wenke | College of Chemistry and Materials Science, Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi'an 710127, China | | | LIU Ce | College of Chemistry and Materials Science, Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi'an 710127, China | | | CHEN Wei | College of Chemistry and Materials Science, Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi'an 710127, China | | | KE Hongshan | College of Chemistry and Materials Science, Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi'an 710127, China | | | ZENG Fanlong | College of Chemistry and Materials Science, Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi'an 710127, China | | | LEI Yibo | College of Chemistry and Materials Science, Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi'an 710127, China | | | LI Anyang | College of Chemistry and Materials Science, Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi'an 710127, China | liay@nwu.edu.cn | | WANG Wenyuan | College of Chemistry and Materials Science, Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi'an 710127, China | wangwy@nwu.edu.cn |
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| Abstract: The ultra-bulky and stable monodentate amino groups can provide effective kinetic protection during the preparation of low-coordinate transition metal complexes, thereby preventing oligomerization. In this work, the ultrabulky sodium hexa-isopropyl disilylamide (2) was synthesized for the first time by the reaction of silylamine and sodium amide, and the crystal structures of 2-THF and 2-Tol, which are complexes of 2 coordinated by tetrahydrofuran (THF) or toluene (Tol), respectively, were characterized. Then, the diamino iron[Fe(Ⅱ) (N(SiiPr3)2)2] (3) and diamino dichloro-bis-chromium[Cr(Ⅱ)(N(SiiPr3)2) Cl]2 (4) were synthesized through the salt metathesis reaction of 2 with the corresponding transition metal halides FeCl2 and CrCl2. Due to the steric hindrance of the ultra-bulky amino groups, complex 3 presents a nearly linear geometry, with the N-Fe-N bond angle of 178.10°. Complex 4 is a dimer of monoamino chromium(Ⅱ) chloride; the three-coordinate Cr(Ⅱ) ions form a {Cr2Cl2} rhombic core via two Clbridges. The improved iCAS method (imposed automatic selection and localization of complete active spaces) was used to calculate the molecular orbitals of 3 and 4 to logically describe the strongly correlated systems of electrons of the low-coordinate sphere of transition metals. The calculation shows that the bonding contribution of 3 mainly consists of the two Fe-Nσ bonds, and the charge of Fe (+1.03) and N (-1.21) confirms a strong ionic coordination environment. The Fe-N π-bonding is not evident. The quintuplet high-spin Fe has one doubly occupied orbital and four singly occupied orbitals, originating from the 3d orbitals of Fe. The six fully occupied molecular orbitals of 4 correspond to two Cr-N σ bonds, two p-type lone pairs on Cl atoms, and two p-type lone pairs on N atoms. Two Cr atoms have eight high-energy d electrons, each in a singly occupied active orbital, and one of them exhibits Cr… Cr interaction. |
| Keywords: iron chromium ultra-bulky silylamino group low-coordination |
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| ZHENG Wenke,LIU Ce,CHEN Wei,KE Hongshan,ZENG Fanlong,LEI Yibo,LI Anyang,WANG Wenyuan.Synthesis and bonding analysis of low-coordinate Fe and Cr complexes with ultra-bulky silylamino groups[J].Chinese Journal of Inorganic Chemistry,2025,41(7):1285-1293. |
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