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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Mechanistic Insights into the Stepwise Assembly of Ruthenium(II) Tris-heteroleptic Compounds

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Author(s):
Mueller, Andressa V. [1] ; Polo, Andre S. [1]
Total Authors: 2
Affiliation:
[1] Univ Fed ABC UFABC, Ctr Ciencias Nat & Humanas, Ave Estados 5001, BR-09210580 Santo Andre, SP - Brazil
Total Affiliations: 1
Document type: Journal article
Source: Inorganic Chemistry; v. 57, n. 21, p. 13829-13839, NOV 5 2018.
Web of Science Citations: 2
Abstract

The ruthenium(II) tris-heteroleptic compounds cis-{[}Ru(NN)(dcbH(2))(NCS)(2)], NN = polypyridyl ligand and dcbH(2) = 2,2'-bipyridine-4,4'-dicarboxylic acid, can be synthesized by a one-pot route starting from {[}Ru(p-cymene)Cl-2](2), followed by the sequential addition of ligands. In this work, each synthetic step for the cis-{[}Ru(R-phen)(dcbH(2))(NCS)(2)] (R = H, Me, Ph, MeO, or Cl) preparation was individually investigated, aiming to identify reaction intermediates and to establish correlations among temperature, reaction time, reactant concentration, and the identity of the substituent of the polypyridyl ligand with the kinetics of the reactions and distribution of the products. The first step is the cleavage of {[}Ru(p-cymene)Cl-2](2), followed by the coordination of R-phen via an associative mechanism and establishment of a direct correlation between the electron-donating or electron-withdrawing character of R and the reaction rates. The second step is the conversion of {[}Ru(R-phen)(p-cymene)Cl]Cl to cis-{[}Ru(R-phen)(dcbH(2))Cl-2], and the rate-determining step is the formation of the intermediate {[}Ru(R-phen)Cl-2], which exhibits a low dependence on R. The last step is the substitution of Cl- by NCS-, and the N-bound isomer is the major product. The reaction temperature, time, and identity of R influence the relative distribution of the linkage isomers. The comprehension of each of these processes is a key factor to develop new strategies to optimize the one-pot synthetic route. (AU)

FAPESP's process: 16/24020-9 - Evaluation of processes photoassisted by Ru(II) and Re(I) polypyridyl compounds
Grantee:Andressa Vidal Muller
Support Opportunities: Scholarships in Brazil - Doctorate
FAPESP's process: 16/21993-6 - Evaluation of Ru(II) and Re(I) polypyridyl compounds on photoactive devices
Grantee:André Sarto Polo
Support Opportunities: Regular Research Grants