Isolation and Reactivity of Tetrylene-Tetrylone-Iron Complexes Supported by Bis(N-Heterocyclic Imine) Ligands

Xuan Xuan Zhao; Tibor Szilvási; Franziska Hanusch; John A. Kelly; Shiori Fujimori; Shigeyoshi Inoue

doi:10.1002/anie.202208930

Isolation and Reactivity of Tetrylene-Tetrylone-Iron Complexes Supported by Bis(N-Heterocyclic Imine) Ligands

Xuan Xuan Zhao, Tibor Szilvási, Franziska Hanusch, John A. Kelly, Shiori Fujimori, Shigeyoshi Inoue

Chair of Silicon Chemistry

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

13 Scopus citations

Abstract

The germanium iron carbonyl complex 3 was prepared by the reaction of dimeric chloro(imino)germylene [IPrNGeCl]₂ (IPrN=bis(2,6-diisopropylphenyl)imidazolin-2-iminato) with one equivalent of Collman's reagent (Na₂Fe(CO)₄) at room temperature. Similarly, the reaction of chloro(imino)stannylene [IPrNSnCl]₂ with Na₂Fe(CO)₄ (1 equiv) resulted in the Fe(CO)₄-bridged bis(stannylene) complex 4. We observed reversible formation of bis(tetrylene) and tetrylene-tetrylone character in complexes 3 vs. 5 and 4 vs. 6, which was supported by DFT calculations. Moreover, the Li/Sn/Fe trimetallic complex 12 has been isolated from the reaction of [IPrNSnCl]₂ with cyclopentadienyl iron dicarbonyl anion. The computational analysis further rationalizes the reduction pathway from these chlorotetrylenes to the corresponding complexes.

Original language	English
Journal	Angewandte Chemie International Edition in English
DOIs	https://doi.org/10.1002/anie.202208930
State	Published - 26 Sep 2022

Keywords

Germanium
Iron Carbonyl Complexes
Low-Valent Compounds
Tin
Trimetallic Complexes

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10.1002/anie.202208930

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title = "Isolation and Reactivity of Tetrylene-Tetrylone-Iron Complexes Supported by Bis(N-Heterocyclic Imine) Ligands",

abstract = "The germanium iron carbonyl complex 3 was prepared by the reaction of dimeric chloro(imino)germylene [IPrNGeCl]2 (IPrN=bis(2,6-diisopropylphenyl)imidazolin-2-iminato) with one equivalent of Collman's reagent (Na2Fe(CO)4) at room temperature. Similarly, the reaction of chloro(imino)stannylene [IPrNSnCl]2 with Na2Fe(CO)4 (1 equiv) resulted in the Fe(CO)4-bridged bis(stannylene) complex 4. We observed reversible formation of bis(tetrylene) and tetrylene-tetrylone character in complexes 3 vs. 5 and 4 vs. 6, which was supported by DFT calculations. Moreover, the Li/Sn/Fe trimetallic complex 12 has been isolated from the reaction of [IPrNSnCl]2 with cyclopentadienyl iron dicarbonyl anion. The computational analysis further rationalizes the reduction pathway from these chlorotetrylenes to the corresponding complexes.",

keywords = "Germanium, Iron Carbonyl Complexes, Low-Valent Compounds, Tin, Trimetallic Complexes",

author = "Zhao, {Xuan Xuan} and Tibor Szilv{\'a}si and Franziska Hanusch and Kelly, {John A.} and Shiori Fujimori and Shigeyoshi Inoue",

note = "Publisher Copyright: {\textcopyright} 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

year = "2022",

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doi = "10.1002/anie.202208930",

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T1 - Isolation and Reactivity of Tetrylene-Tetrylone-Iron Complexes Supported by Bis(N-Heterocyclic Imine) Ligands

AU - Zhao, Xuan Xuan

AU - Szilvási, Tibor

AU - Hanusch, Franziska

AU - Kelly, John A.

AU - Fujimori, Shiori

AU - Inoue, Shigeyoshi

PY - 2022/9/26

Y1 - 2022/9/26

N2 - The germanium iron carbonyl complex 3 was prepared by the reaction of dimeric chloro(imino)germylene [IPrNGeCl]2 (IPrN=bis(2,6-diisopropylphenyl)imidazolin-2-iminato) with one equivalent of Collman's reagent (Na2Fe(CO)4) at room temperature. Similarly, the reaction of chloro(imino)stannylene [IPrNSnCl]2 with Na2Fe(CO)4 (1 equiv) resulted in the Fe(CO)4-bridged bis(stannylene) complex 4. We observed reversible formation of bis(tetrylene) and tetrylene-tetrylone character in complexes 3 vs. 5 and 4 vs. 6, which was supported by DFT calculations. Moreover, the Li/Sn/Fe trimetallic complex 12 has been isolated from the reaction of [IPrNSnCl]2 with cyclopentadienyl iron dicarbonyl anion. The computational analysis further rationalizes the reduction pathway from these chlorotetrylenes to the corresponding complexes.

AB - The germanium iron carbonyl complex 3 was prepared by the reaction of dimeric chloro(imino)germylene [IPrNGeCl]2 (IPrN=bis(2,6-diisopropylphenyl)imidazolin-2-iminato) with one equivalent of Collman's reagent (Na2Fe(CO)4) at room temperature. Similarly, the reaction of chloro(imino)stannylene [IPrNSnCl]2 with Na2Fe(CO)4 (1 equiv) resulted in the Fe(CO)4-bridged bis(stannylene) complex 4. We observed reversible formation of bis(tetrylene) and tetrylene-tetrylone character in complexes 3 vs. 5 and 4 vs. 6, which was supported by DFT calculations. Moreover, the Li/Sn/Fe trimetallic complex 12 has been isolated from the reaction of [IPrNSnCl]2 with cyclopentadienyl iron dicarbonyl anion. The computational analysis further rationalizes the reduction pathway from these chlorotetrylenes to the corresponding complexes.

KW - Germanium

KW - Iron Carbonyl Complexes

KW - Low-Valent Compounds

KW - Tin

KW - Trimetallic Complexes

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U2 - 10.1002/anie.202208930

DO - 10.1002/anie.202208930

M3 - Article

C2 - 35925668

AN - SCOPUS:85137022089

SN - 1433-7851

JO - Angewandte Chemie International Edition in English

JF - Angewandte Chemie International Edition in English

ER -

Isolation and Reactivity of Tetrylene-Tetrylone-Iron Complexes Supported by Bis(N-Heterocyclic Imine) Ligands

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