Synthesis and characterisation of palladium(II) complexes with hybrid phosphinoferrocene ligands bearing additional O-donor substituents

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F19%3A10393736" target="_blank" >RIV/00216208:11310/19:10393736 - isvavai.cz</a>

Výsledek na webu

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

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c9nj00298g" target="_blank" >10.1039/c9nj00298g</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Synthesis and characterisation of palladium(II) complexes with hybrid phosphinoferrocene ligands bearing additional O-donor substituents

Popis výsledku v původním jazyce

While 1,1&apos;-bis(diphenylphosphino) ferrocene (dppf) is widely used as a ligand in coordination chemistry and catalysis, its congeners with oxygen-containing functional groups have long been overlooked. Accordingly, we studied the coordination behaviour in Pd(II) complexes of three phosphinoferrocene ligands bearing secondary O-donor groups, Ph2PfcR, wherein R = CHO (1), Ac (2) and CMe2(OH) (3), and fc = ferrocene-1,1&apos;-diyl. Depending on the stoichiometry, reactions of 1-3 (L) with [PdCl2(cod)] (cod = eta(2):eta(2)-cycloocta-1,5-diene) produced the respective mono- and dipalladium complexes, trans[ PdCl2(L-kappa P)(2)] and trans-[PdCl(mu-Cl)(L-kappa P)](2). Compound [PdCl(mu-Cl)(3-kappa P)](2) was found to dehydrate readily, giving rise to [PdCl(mu-Cl)(Ph(2)PfcC(Me)=CH2-kappa P)](2). Furthermore, ligands 1-3 cleaved [(L-NC)Pd(mu-Cl)](2) (L-NC = 2-((dimethylamino-kappa N)methyl)phenyl-kappa C-1), yielding [(L-NC)PdCl(L-kappa P)], which were converted into the cationic complexes [(L-NC)PdCl(L)]X (L/X = 1/PF6, 2/SbF6, 3/PF6). Compounds with ligands 1 and 2 were structurally authenticated as stable bis-chelate complexes. In contrast, the product featuring ligand 3 was rather unstable and converted into [(L-NC)Pd(AcOEt-kappa O)(3-kP)][PF6] upon recrystallisation. Weak oxygen coordination was confirmed via reactions of [(L-NC)PdCl(L)] X with (PhCH2NEt3)Cl in which the parent chloride complexes were regenerated, and this was further corroborated by DFT computations. Our findings, pointing to hemilabile coordination of 1-3, are relevant for catalysis because de-coordination of the weaker binding O-donor moiety may open a vacant site for a substrate, thereby enhancing the catalytic properties of metal complexes with ligands of this type.

Název v anglickém jazyce

Synthesis and characterisation of palladium(II) complexes with hybrid phosphinoferrocene ligands bearing additional O-donor substituents

Popis výsledku anglicky

While 1,1&apos;-bis(diphenylphosphino) ferrocene (dppf) is widely used as a ligand in coordination chemistry and catalysis, its congeners with oxygen-containing functional groups have long been overlooked. Accordingly, we studied the coordination behaviour in Pd(II) complexes of three phosphinoferrocene ligands bearing secondary O-donor groups, Ph2PfcR, wherein R = CHO (1), Ac (2) and CMe2(OH) (3), and fc = ferrocene-1,1&apos;-diyl. Depending on the stoichiometry, reactions of 1-3 (L) with [PdCl2(cod)] (cod = eta(2):eta(2)-cycloocta-1,5-diene) produced the respective mono- and dipalladium complexes, trans[ PdCl2(L-kappa P)(2)] and trans-[PdCl(mu-Cl)(L-kappa P)](2). Compound [PdCl(mu-Cl)(3-kappa P)](2) was found to dehydrate readily, giving rise to [PdCl(mu-Cl)(Ph(2)PfcC(Me)=CH2-kappa P)](2). Furthermore, ligands 1-3 cleaved [(L-NC)Pd(mu-Cl)](2) (L-NC = 2-((dimethylamino-kappa N)methyl)phenyl-kappa C-1), yielding [(L-NC)PdCl(L-kappa P)], which were converted into the cationic complexes [(L-NC)PdCl(L)]X (L/X = 1/PF6, 2/SbF6, 3/PF6). Compounds with ligands 1 and 2 were structurally authenticated as stable bis-chelate complexes. In contrast, the product featuring ligand 3 was rather unstable and converted into [(L-NC)Pd(AcOEt-kappa O)(3-kP)][PF6] upon recrystallisation. Weak oxygen coordination was confirmed via reactions of [(L-NC)PdCl(L)] X with (PhCH2NEt3)Cl in which the parent chloride complexes were regenerated, and this was further corroborated by DFT computations. Our findings, pointing to hemilabile coordination of 1-3, are relevant for catalysis because de-coordination of the weaker binding O-donor moiety may open a vacant site for a substrate, thereby enhancing the catalytic properties of metal complexes with ligands of this type.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA15-11571S" target="_blank" >GA15-11571S: Nesymetrické fosfinoferrocenové donory</a><br>

Návaznosti

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

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

New Journal of Chemistry

ISSN

1144-0546

e-ISSN

—

Svazek periodika

43

Číslo periodika v rámci svazku

11

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

8

Strana od-do

4463-4470

Kód UT WoS článku

000460972700016

EID výsledku v databázi Scopus

2-s2.0-85062865154