Versatile coordination and C-H activation of a multi-donor phosphinoferrocene carboxamide ligand in Pd(II) complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F19%3A10401683" target="_blank" >RIV/00216208:11310/19:10401683 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=QPI_m27CwI" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=QPI_m27CwI</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c9dt03646f" target="_blank" >10.1039/c9dt03646f</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Versatile coordination and C-H activation of a multi-donor phosphinoferrocene carboxamide ligand in Pd(II) complexes

Popis výsledku v původním jazyce

A multi-donor phosphinoferrocene carboxamide, FcCONHCH(2)CH(2)PPh(2) (1, Fc = ferrocenyl), was prepared, converted into the corresponding phosphine oxide 1O and phosphine selenide 1Se and, mainly, studied as a ligand in Pd(II) complexes. In its native form, amide 1 preferentially coordinated soft Pd(II) as a simple phosphine, giving rise to mixtures of cis and trans-[PdX2(1-kappa P)(2)] (2; X = Cl (a), Br (b), and I (c)), wherein the isomer ratios depended on the auxiliary halide ligand or, alternatively, to the complex [(L-NC)PdCl(1-kappa P)] (6, L-NC = 2-[(dimethylamino)methyl-kappa N]phenyl-kappa C-1). This coordination mode was nevertheless easily changed when creating a vacant coordination site at the palladium. Thus, treatment of 2a with NH4[PF6] in the presence of free 1 produced [PdCl(1-kappa P)(3)][PF6] (3), while complete halogen removal with a Ag(i) salt led to cationic complexes cis-[Pd(1-kappa O-2,P)(2)]X-2 (4, X = CF3SO3 (a), ClO4 (b), BF4 (c)) or [(L-NC)Pd(1-kappa O-2,P)]X (7a and 7b), containing seven-membered O,P-chelate rings. In contrast, amide nitrogen deprotonation with KOt-Bu followed by spontaneous intramolecular halogen substitution resulted in the transformation of 6 into the chelate complex [(L-NC)Pd{(1 - H)-kappa N-2,P}] (8) featuring a five-membered N,P-chelate ring, and in the conversion of 2a and 2b into the product of C-H bond activation [Pd{Fe(eta (5)-C5H3CONCH2CH2PPh2-kappa C-3,N,P)(eta (5)-C5H5)}(1-kappa P)] (5), with doubly chelating deprotonated 1. Importantly, complexes 2-4-5 and 6-7-8 were mutually interconverted in triads (by protonation/deprotonation and by halide addition/abstraction), which highlights the flexible coordination and chemical stability of ligand 1. The crystal structures of 1O1/2H(2)O, trans-2aMeCN, trans-2b3C(2)H(4)Cl(2), trans-2c2.5C(2)H(4)Cl(2), 4aCH(2)Cl(2), 53CHCl(3)Et(2)O, and 8 were determined by single-crystal X-ray diffraction analysis, and the representative compounds were studied by cyclic voltammetry.

Název v anglickém jazyce

Versatile coordination and C-H activation of a multi-donor phosphinoferrocene carboxamide ligand in Pd(II) complexes

Popis výsledku anglicky

A multi-donor phosphinoferrocene carboxamide, FcCONHCH(2)CH(2)PPh(2) (1, Fc = ferrocenyl), was prepared, converted into the corresponding phosphine oxide 1O and phosphine selenide 1Se and, mainly, studied as a ligand in Pd(II) complexes. In its native form, amide 1 preferentially coordinated soft Pd(II) as a simple phosphine, giving rise to mixtures of cis and trans-[PdX2(1-kappa P)(2)] (2; X = Cl (a), Br (b), and I (c)), wherein the isomer ratios depended on the auxiliary halide ligand or, alternatively, to the complex [(L-NC)PdCl(1-kappa P)] (6, L-NC = 2-[(dimethylamino)methyl-kappa N]phenyl-kappa C-1). This coordination mode was nevertheless easily changed when creating a vacant coordination site at the palladium. Thus, treatment of 2a with NH4[PF6] in the presence of free 1 produced [PdCl(1-kappa P)(3)][PF6] (3), while complete halogen removal with a Ag(i) salt led to cationic complexes cis-[Pd(1-kappa O-2,P)(2)]X-2 (4, X = CF3SO3 (a), ClO4 (b), BF4 (c)) or [(L-NC)Pd(1-kappa O-2,P)]X (7a and 7b), containing seven-membered O,P-chelate rings. In contrast, amide nitrogen deprotonation with KOt-Bu followed by spontaneous intramolecular halogen substitution resulted in the transformation of 6 into the chelate complex [(L-NC)Pd{(1 - H)-kappa N-2,P}] (8) featuring a five-membered N,P-chelate ring, and in the conversion of 2a and 2b into the product of C-H bond activation [Pd{Fe(eta (5)-C5H3CONCH2CH2PPh2-kappa C-3,N,P)(eta (5)-C5H5)}(1-kappa P)] (5), with doubly chelating deprotonated 1. Importantly, complexes 2-4-5 and 6-7-8 were mutually interconverted in triads (by protonation/deprotonation and by halide addition/abstraction), which highlights the flexible coordination and chemical stability of ligand 1. The crystal structures of 1O1/2H(2)O, trans-2aMeCN, trans-2b3C(2)H(4)Cl(2), trans-2c2.5C(2)H(4)Cl(2), 4aCH(2)Cl(2), 53CHCl(3)Et(2)O, and 8 were determined by single-crystal X-ray diffraction analysis, and the representative compounds were studied by cyclic voltammetry.

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/GA19-09334S" target="_blank" >GA19-09334S: Nekonvenční ferrocenové fosfiny</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

Dalton Transactions

ISSN

1477-9226

e-ISSN

—

Svazek periodika

48

Číslo periodika v rámci svazku

43

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

14

Strana od-do

16412-16425

Kód UT WoS článku

000496185000027

EID výsledku v databázi Scopus

2-s2.0-85074553142