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

Professur für Siliciumchemie

Publikation: Beitrag in Fachzeitschrift › Artikel › Begutachtung

15 Zitate (Scopus)

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.

Originalsprache	Englisch
Seiten (von - bis)	23274-23280
Seitenumfang	7
Fachzeitschrift	Angewandte Chemie International Edition in English
Jahrgang	60
Ausgabenummer	43
DOIs	https://doi.org/10.1002/anie.202108146
Publikationsstatus	Veröffentlicht - 18 Okt. 2021

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10.1002/anie.202108146

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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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AU - Hanusch, Franziska

AU - Munz, Dominik

AU - Sutter, Jörg

AU - Meyer, Karsten

AU - Inoue, Shigeyoshi

PY - 2021/10/18

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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.

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KW - gold

KW - iron

KW - silicon

KW - zwitterionic complexes

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

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