Changing the properties of monodentate and P,C-chelating ferrocenyl-substituted 1,2,3-triazol-5-ylidene ligands through an inserted carbonyl moiety

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F25%3A10497841" target="_blank" >RIV/00216208:11310/25:10497841 - isvavai.cz</a>

Result on the web

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=SneBXOCue3" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=SneBXOCue3</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d5dt00545k" target="_blank" >10.1039/d5dt00545k</a>

Result language

angličtina

Original language name

Changing the properties of monodentate and P,C-chelating ferrocenyl-substituted 1,2,3-triazol-5-ylidene ligands through an inserted carbonyl moiety

Original language description

Triazolylidenes derived from readily accessible triazoles are useful ligands for coordination chemistry and catalysis. This work describes the synthesis of Group 11 metal complexes of new ferrocenyl-substituted triazolylidene ligands in which the ferrocene and triazolylidene moieties are separated by a carbonyl linker. In particular, complexes of types [MCl(FcC(O){CCN(Mes)NN(Me)}-κC(5))] (M = Cu or Au; Fc = ferrocenyl) and [M(FcC(O){CCN(Mes)NN(Me)}-κC(5))2][BF4] (M = Cu, Ag, or Au) were prepared from FcC(O)CCH and characterised by spectroscopic methods, X-ray diffraction analysis and cyclic voltammetry. Using a similar strategy, the Pd(II) complex trans-[PdCl2(Ph2PfcC(O){CCN(Mes)NN(Me)}-κ(2)P,C(5))] (fc = ferrocene-1,1&apos;-diyl) was synthesised and analogously characterised. The phosphinocarbene ligand in this compound coordinates as a trans P,C-chelating ligand, unlike its analogues that lack the C[double bond, length as m-dash]O spacer and similar compounds that combine the phosphine and carbene donor groups on the ferrocene scaffold. The influence of the carbonyl spacer was evaluated in a pair of Pd(II) bis-carbene complexes, [PdBr2({C(Fc)CN(Mes)NN(Me)}-κC5)(iPr2-bimy)] and [PdBr2(FcC(O){CCN(Mes)NN(Me)}-κC(5))(iPr2-bimy)] (iPr2-bimy = 1,3-diisopropyl-1,3-dihydro-2H-benzimidazol-2-ylidene), by Huynh&apos;s electronic parameters and the Fe(II)/Fe(III) redox potential from cyclic voltammetry, which suggested an electron density decrease at the ferrocenyl group and decreased σ donor ability of the triazolylidene moiety upon introduction of the C=O linker. The Group 11 metal complexes were tested as catalysts for the metal-catalysed cyclisation of N-propargylbenzamide into 2-phenyl-5-methylene-4,5-dihydrooxazole. Among them, the chlorogold complex activated with a silver salt achieved the best results.

Czech name

—

Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10402 - Inorganic and nuclear chemistry

Project

<a href="/en/project/GA23-06718S" target="_blank" >GA23-06718S: Rigid and functional ferrocene phosphines</a><br>

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2025

Confidentiality

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

Name of the periodical

Dalton Transactions

ISSN

1477-9226

e-ISSN

1477-9234

Volume of the periodical

54

Issue of the periodical within the volume

16

Country of publishing house

GB - UNITED KINGDOM

Number of pages

13

Pages from-to

6563-6575

UT code for WoS article

001453911800001

EID of the result in the Scopus database

2-s2.0-105002687983