The protonation state governs the coordination of phosphinoferrocene guanidines

Result code in 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>

Result on the web

<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>

Result language

angličtina

Original language name

The protonation state governs the coordination of phosphinoferrocene guanidines

Original language description

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.

Czech name

—

Czech description

—

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/GA19-09334S" target="_blank" >GA19-09334S: Uncoventional ferrocene phosphines</a><br>

Continuities

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

Publication year

2021

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

—

Volume of the periodical

50

Issue of the periodical within the volume

41

Country of publishing house

GB - UNITED KINGDOM

Number of pages

10

Pages from-to

14662-14671

UT code for WoS article

000700909900001

EID of the result in the Scopus database

2-s2.0-85118273202