The Dinuclear Zirconocene Complex [(Cp2Zr)2(μ-Me)(μ-C2Ph)] as a Platform for Small Molecule Activation

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F25%3A00619193" target="_blank" >RIV/61388955:_____/25:00619193 - isvavai.cz</a>

Výsledek na webu

<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202500857" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202500857</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.202500857" target="_blank" >10.1002/chem.202500857</a>

Jazyk výsledku

angličtina

Název v původním jazyce

The Dinuclear Zirconocene Complex [(Cp2Zr)2(μ-Me)(μ-C2Ph)] as a Platform for Small Molecule Activation

Popis výsledku v původním jazyce

The dinuclear title compound [(Cp2Zr)2(mu-Me)(mu-C2Ph)] 5 was prepared from a zirconocene alkynyl methyl complex and Rosenthal's zirconocene source [Cp2Zr(py)(eta 2-Me3SiC2SiMe3)] in a formal comproportionation reaction. This complex shows catalytic activity for the dehydrocoupling of amine boranes, with a dinuclear hydride-bridged alkynyl complex 6 being formed as a catalytically relevant species. The structure of this complex was confirmed for the first time by single-crystal X-ray analysis. The reaction of complex 5 with hydrogen results in hydrogenation of the alkynyl ligand, yielding a highly labile trinuclear hydride-bridged complex as a possible intermediate of zirconocene dihydride/ethylbenzene formation. This complex shows an unusual distorted planar tetracoordinate environment at the central carbon atom positioned between the three Zr centers. The reaction of complex 5 with 2-cyanopyridine and acetonitrile is characterized by a reduction of the substrates. The herein reported reactivity of complex 5 demonstrates the remarkable potential of well-established dinuclear zirconocenes to stabilize unusual bond situations, which were analyzed comprehensively using spectroscopic, structural, and computational methods.

Název v anglickém jazyce

The Dinuclear Zirconocene Complex [(Cp2Zr)2(μ-Me)(μ-C2Ph)] as a Platform for Small Molecule Activation

Popis výsledku anglicky

The dinuclear title compound [(Cp2Zr)2(mu-Me)(mu-C2Ph)] 5 was prepared from a zirconocene alkynyl methyl complex and Rosenthal's zirconocene source [Cp2Zr(py)(eta 2-Me3SiC2SiMe3)] in a formal comproportionation reaction. This complex shows catalytic activity for the dehydrocoupling of amine boranes, with a dinuclear hydride-bridged alkynyl complex 6 being formed as a catalytically relevant species. The structure of this complex was confirmed for the first time by single-crystal X-ray analysis. The reaction of complex 5 with hydrogen results in hydrogenation of the alkynyl ligand, yielding a highly labile trinuclear hydride-bridged complex as a possible intermediate of zirconocene dihydride/ethylbenzene formation. This complex shows an unusual distorted planar tetracoordinate environment at the central carbon atom positioned between the three Zr centers. The reaction of complex 5 with 2-cyanopyridine and acetonitrile is characterized by a reduction of the substrates. The herein reported reactivity of complex 5 demonstrates the remarkable potential of well-established dinuclear zirconocenes to stabilize unusual bond situations, which were analyzed comprehensively using spectroscopic, structural, and computational methods.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/EH22_008%2F0004558" target="_blank" >EH22_008/0004558: Pokročilé víceškálové materiály pro nosné klíčové technologie</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

1521-3765

Svazek periodika

31

Číslo periodika v rámci svazku

26

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

9

Strana od-do

e202500857

Kód UT WoS článku

001460490300001

EID výsledku v databázi Scopus

2-s2.0-105002113398