Reaction of [Fe2(CO)8(-CF2)] with AsMe3 and Other Lewis Bases: Syntheses, Crystal Structur
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- 作者：Meritxell DelaVarga ; Wolfgang Petz ; Bernhard Neumü ; ller ; Ramon Costa
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：October 30, 2006
- 年：2006
- 卷：45
- 期：22
- 页码：9053 - 9063
- 全文大小：311K
- 年卷期：v.45,no.22(October 30, 2006)
- ISSN：1520-510X
文摘
The difluorcarbene complex [Fe2(CO)8(
-CF2)] (2) reacts with AsMe3 under CO substitution to give the -CF2containing complexes [Fe2(CO)6(AsMe3)2(-CF2)] (4) and [Fe2(CO)5(AsMe3)3(-CF2)] (5) which have an [Fe2(CO)9]-like structure as shown by X-ray analyses. In the solid state, 4 forms two isomers, 4a and 4b, in a 3 to 1 ratio,which differ in the position of the -CF2 ligand; 4a has a local C2 axis and 4b has C1 symmetry. The Fe-Fedistances in 4 and 5 are 2.47 Å and are the shortest ones found in [Fe2(CO)9]-like compounds. Efforts were alsoundertaken to replace one or more CO groups in 2 by other ligands, such as N (bpy, phen, pzy, etc.) or P donors(dppe, dppm). With dppm, only the CF2 free complex, [Fe2(CO)4(-Ph2PCH2PPh2)2(-CO)] (6), could be detectedand characterized by X-ray analysis. Most of the reactions resulted in the formation of red-brown materials whichwere insoluble in the usual solvents and which could not be characterized. The use of CH2Cl2 during the attemptsto crystallize a product from the reaction of 2 and phen gave [Fe(phen)3]Cl2 (7) in low yields. For 4 and 5, theelectronic structures were analyzed using the atoms in molecules (AIM) theory. No electron density was foundbetween the two iron atoms, and the short contacts can be interpreted in terms of a 
-interaction.
-CF2)] (2) reacts with AsMe3 under CO substitution to give the -CF2containing complexes [Fe2(CO)6(AsMe3)2(-CF2)] (4) and [Fe2(CO)5(AsMe3)3(-CF2)] (5) which have an [Fe2(CO)9]-like structure as shown by X-ray analyses. In the solid state, 4 forms two isomers, 4a and 4b, in a 3 to 1 ratio,which differ in the position of the -CF2 ligand; 4a has a local C2 axis and 4b has C1 symmetry. The Fe-Fedistances in 4 and 5 are 2.47 Å and are the shortest ones found in [Fe2(CO)9]-like compounds. Efforts were alsoundertaken to replace one or more CO groups in 2 by other ligands, such as N (bpy, phen, pzy, etc.) or P donors(dppe, dppm). With dppm, only the CF2 free complex, [Fe2(CO)4(-Ph2PCH2PPh2)2(-CO)] (6), could be detectedand characterized by X-ray analysis. Most of the reactions resulted in the formation of red-brown materials whichwere insoluble in the usual solvents and which could not be characterized. The use of CH2Cl2 during the attemptsto crystallize a product from the reaction of 2 and phen gave [Fe(phen)3]Cl2 (7) in low yields. For 4 and 5, theelectronic structures were analyzed using the atoms in molecules (AIM) theory. No electron density was foundbetween the two iron atoms, and the short contacts can be interpreted in terms of a -interaction.