A Mixed Aryl/Amide Complex of Iron(II)

Robert M. Wolf; Raphael Bühler; Fabrizio E. Napoli; Johannes Stephan; Christian Gemel; Roland A. Fischer

doi:10.1002/zaac.202400150

A Mixed Aryl/Amide Complex of Iron(II)

Robert M. Wolf, Raphael Bühler, Fabrizio E. Napoli, Johannes Stephan, Christian Gemel, Roland A. Fischer

Chair of Inorganic and Organometallic Chemistry

Technical University of Munich

Research output: Contribution to journal › Article › peer-review

Abstract

The combined incorporation of a labile and a stabilizing ligand in a metal-organic precursor is of interest for the synthesis of low valent ligated (hetero)metallic clusters. The heteroleptic aryl/amide iron (II) complex [Fe₂(Mes)₂(BTSA)₂] (1) was synthesized by equimolar mixing of [Fe₂(Mes)₄] with [Fe₂(BTSA)₄]. (VT)-NMR-, UV-Vis- and SC-XRD-analysis combined with DFT calculations revealed a dimeric structure with terminal bis(trimethylsilyl)amide- and bridging mesityl-ligands in solution and as well in the solid phase. The treatment of [Fe₂(BTSA)₄] with the carbenoid group 13 metallo-ligand GaCp* is known to yield simply adducts. In contrast, monitoring the reactions of [Fe₂(Mes)₄] and [Fe₂(Mes)₂(BTSA)₂] (1) with GaCp* by liquid injection field desorption mass spectrometry (LIFDI-MS) suggest formation of a broader variety of bimetallic Fe−Ga-species with iron formally reduced to iron (I) or iron (0). However, the product distribution obtained using the heteroleptic compound 1 indicates combined reactivity of the homoleptic congeners by showing larger species with variations of Fe/Ga ratios towards the formation of Fe/Ga clusters. This blended behavior is assigned to the more labile mesityl ligand and the more stabilizing BTSA-ligand.

Original language	English
Article number	e202400150
Journal	Zeitschrift fur Anorganische und Allgemeine Chemie
Volume	650
Issue number	24
DOIs	https://doi.org/10.1002/zaac.202400150
State	Published - 16 Dec 2024

Keywords

Bimetallics
DFT calculations
Iron complexes
Ligand effects
Transition metals

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10.1002/zaac.202400150

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title = "A Mixed Aryl/Amide Complex of Iron(II)",

abstract = "The combined incorporation of a labile and a stabilizing ligand in a metal-organic precursor is of interest for the synthesis of low valent ligated (hetero)metallic clusters. The heteroleptic aryl/amide iron (II) complex [Fe2(Mes)2(BTSA)2] (1) was synthesized by equimolar mixing of [Fe2(Mes)4] with [Fe2(BTSA)4]. (VT)-NMR-, UV-Vis- and SC-XRD-analysis combined with DFT calculations revealed a dimeric structure with terminal bis(trimethylsilyl)amide- and bridging mesityl-ligands in solution and as well in the solid phase. The treatment of [Fe2(BTSA)4] with the carbenoid group 13 metallo-ligand GaCp* is known to yield simply adducts. In contrast, monitoring the reactions of [Fe2(Mes)4] and [Fe2(Mes)2(BTSA)2] (1) with GaCp* by liquid injection field desorption mass spectrometry (LIFDI-MS) suggest formation of a broader variety of bimetallic Fe−Ga-species with iron formally reduced to iron (I) or iron (0). However, the product distribution obtained using the heteroleptic compound 1 indicates combined reactivity of the homoleptic congeners by showing larger species with variations of Fe/Ga ratios towards the formation of Fe/Ga clusters. This blended behavior is assigned to the more labile mesityl ligand and the more stabilizing BTSA-ligand.",

keywords = "Bimetallics, DFT calculations, Iron complexes, Ligand effects, Transition metals",

author = "Wolf, {Robert M.} and Raphael B{\"u}hler and Napoli, {Fabrizio E.} and Johannes Stephan and Christian Gemel and Fischer, {Roland A.}",

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T1 - A Mixed Aryl/Amide Complex of Iron(II)

AU - Wolf, Robert M.

AU - Bühler, Raphael

AU - Napoli, Fabrizio E.

AU - Stephan, Johannes

AU - Gemel, Christian

AU - Fischer, Roland A.

PY - 2024/12/16

Y1 - 2024/12/16

N2 - The combined incorporation of a labile and a stabilizing ligand in a metal-organic precursor is of interest for the synthesis of low valent ligated (hetero)metallic clusters. The heteroleptic aryl/amide iron (II) complex [Fe2(Mes)2(BTSA)2] (1) was synthesized by equimolar mixing of [Fe2(Mes)4] with [Fe2(BTSA)4]. (VT)-NMR-, UV-Vis- and SC-XRD-analysis combined with DFT calculations revealed a dimeric structure with terminal bis(trimethylsilyl)amide- and bridging mesityl-ligands in solution and as well in the solid phase. The treatment of [Fe2(BTSA)4] with the carbenoid group 13 metallo-ligand GaCp* is known to yield simply adducts. In contrast, monitoring the reactions of [Fe2(Mes)4] and [Fe2(Mes)2(BTSA)2] (1) with GaCp* by liquid injection field desorption mass spectrometry (LIFDI-MS) suggest formation of a broader variety of bimetallic Fe−Ga-species with iron formally reduced to iron (I) or iron (0). However, the product distribution obtained using the heteroleptic compound 1 indicates combined reactivity of the homoleptic congeners by showing larger species with variations of Fe/Ga ratios towards the formation of Fe/Ga clusters. This blended behavior is assigned to the more labile mesityl ligand and the more stabilizing BTSA-ligand.

AB - The combined incorporation of a labile and a stabilizing ligand in a metal-organic precursor is of interest for the synthesis of low valent ligated (hetero)metallic clusters. The heteroleptic aryl/amide iron (II) complex [Fe2(Mes)2(BTSA)2] (1) was synthesized by equimolar mixing of [Fe2(Mes)4] with [Fe2(BTSA)4]. (VT)-NMR-, UV-Vis- and SC-XRD-analysis combined with DFT calculations revealed a dimeric structure with terminal bis(trimethylsilyl)amide- and bridging mesityl-ligands in solution and as well in the solid phase. The treatment of [Fe2(BTSA)4] with the carbenoid group 13 metallo-ligand GaCp* is known to yield simply adducts. In contrast, monitoring the reactions of [Fe2(Mes)4] and [Fe2(Mes)2(BTSA)2] (1) with GaCp* by liquid injection field desorption mass spectrometry (LIFDI-MS) suggest formation of a broader variety of bimetallic Fe−Ga-species with iron formally reduced to iron (I) or iron (0). However, the product distribution obtained using the heteroleptic compound 1 indicates combined reactivity of the homoleptic congeners by showing larger species with variations of Fe/Ga ratios towards the formation of Fe/Ga clusters. This blended behavior is assigned to the more labile mesityl ligand and the more stabilizing BTSA-ligand.

KW - Bimetallics

KW - DFT calculations

KW - Iron complexes

KW - Ligand effects

KW - Transition metals

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JF - Zeitschrift fur Anorganische und Allgemeine Chemie

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M1 - e202400150

ER -

A Mixed Aryl/Amide Complex of Iron(II)

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Keywords

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