The protonation state governs the coordination of phosphinoferrocene guanidines

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F21%3A10434113" target="_blank" >RIV/00216208:11310/21:10434113 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=ug2fFemy0y" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=ug2fFemy0y</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d1dt02884g" target="_blank" >10.1039/d1dt02884g</a>

Jazyk výsledku

angličtina

Název v původním jazyce

The protonation state governs the coordination of phosphinoferrocene guanidines

Popis výsledku v původním jazyce

Compared to phosphines with guanidinium tags, studied as polar ligands for aqueous catalysis, their counterparts bearing guanidine substituents received only limited attention. This contribution focuses on the coordination of phosphinoferrocene guanidine Ph(2)PfcNC(NHiPr)(2) (1(iPr), fc = ferrocene-1,1&apos;-diyl) as a hybrid, P,N-donor ligand to Group 10 metals. In its native state, 1(iPr) coordinated as a P,N-chelating ligand, affording [M(X)(Y)(1(iPr)-κ(2)P,N)] (M/X/Y = Pd/Cl/Cl, Pd/Br/4-C6H4CN, Pt/Cl/Cl; the corresponding Ni(II) complex was not isolated). While [PdCl2(1(iPr)-κ(2)P,N)] converted into [PdCl(1(iPr)-κ(3)Fe,P,N)](+) species with Fe-Pd interaction, upon chloride removal, the analogous Pt(II) complex dimerised into [Pt-2(μ-Cl)(2)(1(iPr)-κ(2)P,N)(2)](2+). Deprotonation of [PdCl2(1(iPr)-κ(2)P,N)] produced a unique, doubly chelating phosphinoguanidinate complex [PdCl{(1(iPr)-H)-κ(3)P,N,N&apos;}], which was smoothly converted into [Pd(MeCN){(1(iPr)-H)-κ(3)P,N,N&apos;}][SbF6]. The latter, a convenient starting material for substitution reactions, was used to prepare either [Pd(L){(1(iPr)-H)-κ(3)P,N,N&apos;}][SbF6] (L = 4-(dimethylamino)pyridine and 2-phenylpyridine), by simple substitution, or the hydroxide and acetylacetonate (acac) complexes, [Pd-2(μ-OH)(2)(1(iPr)-κ(2)P,N)(2)][SbF6](2) and [Pd(acac)(1(iPr)-κ(2)P,N)][SbF6], by substitution with concomitant proton transfer. In contrast, protonation of the guanidine moiety prevented its coordination, as shown in reactions of the salts (1(iPr)H)Cl and (1(iPr)H)[SbF6]. Depending on the metal-to-ligand ratio, adding (1(iPr)H)[SbF6] to [PdCl2(MeCN)(2)] produced [Pd2Cl2(μ-Cl)(2)(1(iPr)H-κP)(2)][SbF6](2) or [PdCl2(1(iPr)H-κP)(2)][SbF6](2). Analogous reactions involving (1(iPr)H)Cl were more complicated due to competing coordination of the chloride anion, leading to (in addition to other compounds) the zwitterionic complex [PdCl3(1(iPr)H-κP)], which was alternatively obtained by selective protonation of [PdCl2(1(iPr)-κ(2)P,N)] with HCl. Apparently, the protonation state of the guanidine moiety controls the coordination behaviour of phosphinoferrocene guanidines.

Název v anglickém jazyce

The protonation state governs the coordination of phosphinoferrocene guanidines

Popis výsledku anglicky

Compared to phosphines with guanidinium tags, studied as polar ligands for aqueous catalysis, their counterparts bearing guanidine substituents received only limited attention. This contribution focuses on the coordination of phosphinoferrocene guanidine Ph(2)PfcNC(NHiPr)(2) (1(iPr), fc = ferrocene-1,1&apos;-diyl) as a hybrid, P,N-donor ligand to Group 10 metals. In its native state, 1(iPr) coordinated as a P,N-chelating ligand, affording [M(X)(Y)(1(iPr)-κ(2)P,N)] (M/X/Y = Pd/Cl/Cl, Pd/Br/4-C6H4CN, Pt/Cl/Cl; the corresponding Ni(II) complex was not isolated). While [PdCl2(1(iPr)-κ(2)P,N)] converted into [PdCl(1(iPr)-κ(3)Fe,P,N)](+) species with Fe-Pd interaction, upon chloride removal, the analogous Pt(II) complex dimerised into [Pt-2(μ-Cl)(2)(1(iPr)-κ(2)P,N)(2)](2+). Deprotonation of [PdCl2(1(iPr)-κ(2)P,N)] produced a unique, doubly chelating phosphinoguanidinate complex [PdCl{(1(iPr)-H)-κ(3)P,N,N&apos;}], which was smoothly converted into [Pd(MeCN){(1(iPr)-H)-κ(3)P,N,N&apos;}][SbF6]. The latter, a convenient starting material for substitution reactions, was used to prepare either [Pd(L){(1(iPr)-H)-κ(3)P,N,N&apos;}][SbF6] (L = 4-(dimethylamino)pyridine and 2-phenylpyridine), by simple substitution, or the hydroxide and acetylacetonate (acac) complexes, [Pd-2(μ-OH)(2)(1(iPr)-κ(2)P,N)(2)][SbF6](2) and [Pd(acac)(1(iPr)-κ(2)P,N)][SbF6], by substitution with concomitant proton transfer. In contrast, protonation of the guanidine moiety prevented its coordination, as shown in reactions of the salts (1(iPr)H)Cl and (1(iPr)H)[SbF6]. Depending on the metal-to-ligand ratio, adding (1(iPr)H)[SbF6] to [PdCl2(MeCN)(2)] produced [Pd2Cl2(μ-Cl)(2)(1(iPr)H-κP)(2)][SbF6](2) or [PdCl2(1(iPr)H-κP)(2)][SbF6](2). Analogous reactions involving (1(iPr)H)Cl were more complicated due to competing coordination of the chloride anion, leading to (in addition to other compounds) the zwitterionic complex [PdCl3(1(iPr)H-κP)], which was alternatively obtained by selective protonation of [PdCl2(1(iPr)-κ(2)P,N)] with HCl. Apparently, the protonation state of the guanidine moiety controls the coordination behaviour of phosphinoferrocene guanidines.

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

2021

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

50

Číslo periodika v rámci svazku

41

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

10

Strana od-do

14662-14671

Kód UT WoS článku

000700909900001

EID výsledku v databázi Scopus

2-s2.0-85118273202