A Zwitterionic Heterobimetallic Gold–Iron Complex Supported by Bis(N-Heterocyclic Imine)Silyliumylidene

Franziska Hanusch; Dominik Munz; Jörg Sutter; Karsten Meyer; Shigeyoshi Inoue

doi:10.1002/anie.202108146

A Zwitterionic Heterobimetallic Gold–Iron Complex Supported by Bis(N-Heterocyclic Imine)Silyliumylidene

Franziska Hanusch, Dominik Munz, Jörg Sutter, Karsten Meyer, Shigeyoshi Inoue

Associate Professorship of Silicon Chemistry

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

16 Scopus citations

Abstract

The facile synthesis of the first bis-N-heterocyclic imine-stabilized chlorosilyliumylidene 1 is reported. Remarkably, consecutive reaction of 1 with PPh₃AuCl and K₂Fe(CO)₄ gives rise to the unique heterobimetallic complex 1,2-(^MesNHI)₂-C₂H₄-ClSiAuFe(CO)₄ (4). The overall neutral complex 4 bears an unusual linear Si−Au−Fe structure and a rare anagostic interaction between the d¹⁰-configured gold atom and a CH bond of the mesityl ligand. According to the computational analysis and ⁵⁷Fe Mössbauer spectroscopy, the formal Fe-oxidation state remains at −II. Thus, the electronic structure of 4 is best described as an overall neutral—yet zwitterionic—heterobimetallic “Si(II)⁺-Au(I)⁺-Fe(-II)²⁻”-silyliumylidene complex, derived from double anion exchange. The computational analysis indicates strong hyperconjugative back donation from the gold(I) atom to the silyliumylidene ligand.

Original language	English
Pages (from-to)	23274-23280
Number of pages	7
Journal	Angewandte Chemie International Edition in English
Volume	60
Issue number	43
DOIs	https://doi.org/10.1002/anie.202108146
State	Published - 18 Oct 2021

Keywords

anagostic interactions
gold
iron
silicon
zwitterionic complexes

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title = "A Zwitterionic Heterobimetallic Gold–Iron Complex Supported by Bis(N-Heterocyclic Imine)Silyliumylidene",

abstract = "The facile synthesis of the first bis-N-heterocyclic imine-stabilized chlorosilyliumylidene 1 is reported. Remarkably, consecutive reaction of 1 with PPh3AuCl and K2Fe(CO)4 gives rise to the unique heterobimetallic complex 1,2-(MesNHI)2-C2H4-ClSiAuFe(CO)4 (4). The overall neutral complex 4 bears an unusual linear Si−Au−Fe structure and a rare anagostic interaction between the d10-configured gold atom and a CH bond of the mesityl ligand. According to the computational analysis and 57Fe M{\"o}ssbauer spectroscopy, the formal Fe-oxidation state remains at −II. Thus, the electronic structure of 4 is best described as an overall neutral—yet zwitterionic—heterobimetallic “Si(II)+-Au(I)+-Fe(-II)2−”-silyliumylidene complex, derived from double anion exchange. The computational analysis indicates strong hyperconjugative back donation from the gold(I) atom to the silyliumylidene ligand.",

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author = "Franziska Hanusch and Dominik Munz and J{\"o}rg Sutter and Karsten Meyer and Shigeyoshi Inoue",

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AU - Hanusch, Franziska

AU - Munz, Dominik

AU - Sutter, Jörg

AU - Meyer, Karsten

AU - Inoue, Shigeyoshi

PY - 2021/10/18

Y1 - 2021/10/18

N2 - The facile synthesis of the first bis-N-heterocyclic imine-stabilized chlorosilyliumylidene 1 is reported. Remarkably, consecutive reaction of 1 with PPh3AuCl and K2Fe(CO)4 gives rise to the unique heterobimetallic complex 1,2-(MesNHI)2-C2H4-ClSiAuFe(CO)4 (4). The overall neutral complex 4 bears an unusual linear Si−Au−Fe structure and a rare anagostic interaction between the d10-configured gold atom and a CH bond of the mesityl ligand. According to the computational analysis and 57Fe Mössbauer spectroscopy, the formal Fe-oxidation state remains at −II. Thus, the electronic structure of 4 is best described as an overall neutral—yet zwitterionic—heterobimetallic “Si(II)+-Au(I)+-Fe(-II)2−”-silyliumylidene complex, derived from double anion exchange. The computational analysis indicates strong hyperconjugative back donation from the gold(I) atom to the silyliumylidene ligand.

AB - The facile synthesis of the first bis-N-heterocyclic imine-stabilized chlorosilyliumylidene 1 is reported. Remarkably, consecutive reaction of 1 with PPh3AuCl and K2Fe(CO)4 gives rise to the unique heterobimetallic complex 1,2-(MesNHI)2-C2H4-ClSiAuFe(CO)4 (4). The overall neutral complex 4 bears an unusual linear Si−Au−Fe structure and a rare anagostic interaction between the d10-configured gold atom and a CH bond of the mesityl ligand. According to the computational analysis and 57Fe Mössbauer spectroscopy, the formal Fe-oxidation state remains at −II. Thus, the electronic structure of 4 is best described as an overall neutral—yet zwitterionic—heterobimetallic “Si(II)+-Au(I)+-Fe(-II)2−”-silyliumylidene complex, derived from double anion exchange. The computational analysis indicates strong hyperconjugative back donation from the gold(I) atom to the silyliumylidene ligand.

KW - anagostic interactions

KW - gold

KW - iron

KW - silicon

KW - zwitterionic complexes

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ER -

A Zwitterionic Heterobimetallic Gold–Iron Complex Supported by Bis(N-Heterocyclic Imine)Silyliumylidene

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