Facile Substitution of Bridging SO22- Ligands in Re12 Bioctahedral Cluster Complexes.
Inorg Chem
; 56(20): 12389-12400, 2017 Oct 16.
Article
en En
| MEDLINE
| ID: mdl-28937753
ABSTRACT
Selective substitution of µ-SO22- groups by either O2- or Se2- ions occurs upon heating the bioctahedral rhenium cluster complex K6[Re12CS14(µ-SO2)3(CN)6] in air atmosphere or in the presence of a Se source, respectively, manifesting the remarkable lability of SO22- ligands bound to a transition-metal cluster. A series of compounds based on the new mixed-ligand anions, [Re12CS14(µ-O)3(CN)6]6-, [Re12CS14(µ-Se)3(CN)6]6-, and [Re12CS14(µ-O)3(OH)6]6-, were isolated and their solid-state structures were elucidated by single-crystal X-ray diffraction analysis. Along with the previously reported µ-sulfide clusters, the new species constitute a series of rhenium anionic complexes with the common formula [Re12CS14(µ-Q)3L6]6- (Q = O, S, Se, L = CN-; Q = O, S, L = OH-), within which the total charge and number of cluster valence electrons (CVEs) are constant. The article presents insights into the mechanistic and synthetic aspects of the substitution process, and it comprehensively discusses the influence of inner ligand environment on the structure, spectroscopic characteristics, and electrochemical behavior of the novel compounds.
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Inorg Chem
Año:
2017
Tipo del documento:
Article
País de afiliación:
Rusia