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

17 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
Article number	e202208930
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	39
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

UR - https://www.scopus.com/pages/publications/85137022089

U2 - 10.1002/anie.202208930

DO - 10.1002/anie.202208930

M3 - Article

C2 - 35925668

AN - SCOPUS:85137022089

SN - 1433-7851

VL - 61

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 39

M1 - e202208930

ER -

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

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Keywords

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