Dataset Information

Synthesis of Silsesquioxanes with Substituted Triazole Ring Functionalities and Their Coordination Ability.

ABSTRACT: A synthesis of a series of mono-T₈ and difunctionalized double-decker silsesquioxanes bearing substituted triazole ring(s) has been reported within this work. The catalytic protocol for their formation is based on the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) process. Diverse alkynes were in the scope of our interest-i.e., aryl, hetaryl, alkyl, silyl, or germyl-and the latter was shown to be the first example of terminal germane alkyne which is reactive in the applied process' conditions. From the pallet of 15 compounds, three of them with pyridine-triazole and thiophenyl-triazole moiety attached to T₈ or DDSQ core were verified in terms of their coordinating properties towards selected transition metals, i.e., Pd(II), Pt(II), and Rh(I). The studies resulted in the formation of four SQs based coordination compounds that were obtained in high yields up to 93% and their thorough spectroscopic characterization is presented. To our knowledge, this is the first example of the DDSQ-based molecular complex possessing bidentate pyridine-triazole ligand binding two Pd(II) ions.

SUBMITTER: Rzonsowska M

PROVIDER: S-EPMC7830482 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Synthesis of Silsesquioxanes with Substituted Triazole Ring Functionalities and Their Coordination Ability.

Rzonsowska Monika M Kozakiewicz Katarzyna K Mituła Katarzyna K Duszczak Julia J Kubicki Maciej M Dudziec Beata B

Molecules (Basel, Switzerland) 20210115 2

A synthesis of a series of mono-T<sub>8</sub> and difunctionalized double-decker silsesquioxanes bearing substituted triazole ring(s) has been reported within this work. The catalytic protocol for their formation is based on the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) process. Diverse alkynes were in the scope of our interest-i.e., aryl, hetaryl, alkyl, silyl, or germyl-and the latter was shown to be the first example of terminal germane alkyne which is reactive in the applied pro ...[more]

PMID: 33467746

Similar Datasets

Project description:A series of N(1),N(1),N(3)-tri-substituted benzamidrazones of the general formula [PhC(NHR)=NNMe(2)] (R = Me, n-Pr, i-Pr, n-Bu, Bn, Ph; 1a-f) was synthesized via condensation of 1,1-dimethylhydrazine with the corresponding imidoyl chloride, [PhC(Cl)=NR]. Multinuclear NMR data, and zero-point energy DFT calculations conducted with the B3LYP functional and 6-31G+(d,p) basis set, suggest that these compounds exist as a single tautomer in solution; possessing a weak intramolecular hydrogen bond and a structure dominated by the localised resonance structure ArC(NHR)=N-NMe(2). An X-ray crystallographic study upon PhC(NHPh)=NNMe(2) (1f) demonstrated that this compound adopts an identical tautomer in the solid state. Reactions of [PhC(NHMe)=NNMe(2)] (1a) with [LMCl(2)](2) (M = Ru, L = cymene; M = Rh, Ir, L = Cp*) results in the stoichiometric formation of products of the formula [LM{PhC(=NMe)NHNMe(2)}Cl](+)Cl(-) (2a-c) in which the amidrazone chelates the metal in a κ(2)-N(1),N(3)-coordination mode. Formation of this five-membered chelate occurs with a concomitant tautomerisation of the amidrazone ligand to an alternative tautomer, i.e. [PhC(=NMe)NHNMe(2)], the latter tautomer is expected to be readily energetically accessible based upon the aforementioned DFT calculations. This series of salts may be deprotonated with lithium hexamethyldisilazide to form the corresponding charge neutral complexes [LM{PhC(NMe)=NNMe(2)}] (3a-c). In contrast, the reaction of N(1),N(1),N(3)-tri-substituted benzamidrazones with [(cymene)RuCl(2)](2) in the presence of NaOAc yielded a mixture of cyclometallation (C-H activation) and amidrazone chelation/deprotonation (N-H activation) products. Reaction of 1a yielded an inseparable mixture of products, whilst the reaction of 1c resulted in formation of the cyclometallated product [LM{C(6)H(5)C(=N(i)Pr)NHNMe(2)}] (L = cymene, M = Ru; 4a) in a modest 62% yield. This latter complex could be isolated as a crystalline orange solid, full characterisation including single crystal X-ray diffraction demonstrated that the amidrazone coordinates in a κ(2)-N(2),C-coordination mode.

Dataset Information

Synthesis of Silsesquioxanes with Substituted Triazole Ring Functionalities and Their Coordination Ability.

Publications

Synthesis of Silsesquioxanes with Substituted Triazole Ring Functionalities and Their Coordination Ability.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets