Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.



Mono-substituted amine-oligosilsesquioxanes as functional tools in the Pd(II) coordination chemistry: synthesis and properties

Abstract

Among the broad palette of POSS hybrids, mono-functionalized ones can be considered as attractive starting blocks for further structural expansion. In this paper, we report on their weakly known group represents by N-containing derivatives which have great potential in many areas of organic and coordination chemistry. By using Buchwald-Hartwig amination, and starting from (3-aminopropyl)hepta(isobutyl)octasilsesquioxane and different aryl bromides, we obtained eight novel mono-substituted amine-POSS derivatives via C(sp2)-N bond creation. In the next step, selected hybrids were used in metalation reactions by using palladium acetate. The driving force of this reaction is the formation of the metallacycle entity possessing {Pd[N-H···O-C-O]} core, which is built by POSS attached amine fragments and acetate ligands, which points to non-typical behavior in comparison to the conventional reaction between Pd(OAc)2 and classical amine. The resulting coordination entities show very good solubility, which is not always possible with fully substituted POSS ligands and, what should be emphasized, strongly demanded in potential applications, e.g. in catalysis. Herein, we report on the first palladium compounds containing mono-functionalized amine-POSS ligands, with pseudochelate interaction stabilized by a hydrogen bond. For a detailed picture of the stability of the chelate rings maintained by hydrogen bonds, DFT calculations were carried out. Furthermore, preliminary catalytic behavior of the resulting Pd(II) coordination compounds has been examined in the Suzuki-Miyaura coupling. All obtained compounds were characterized by using EA, NMR (1H, 13C, 29Si), and HR-MS.

Back to tab navigation

Supplementary files

Article information


Submitted
30 Mar 2020
Accepted
21 May 2020
First published
22 May 2020

New J. Chem., 2020, Accepted Manuscript
Article type
Paper

Mono-substituted amine-oligosilsesquioxanes as functional tools in the Pd(II) coordination chemistry: synthesis and properties

K. Piec, S. Kostera, D. Jedrzkiewicz, J. Ejfler and L. John, New J. Chem., 2020, Accepted Manuscript , DOI: 10.1039/D0NJ01568G

Social activity

Search articles by author

Spotlight

Advertisements