Palladium(II), ruthenium(II), and ruthenium(III) complexes of 23-thiaazuliporphyrin: the case of coordination-induced contraction.
PBN-AR
Instytucja
Wydział Chemii (Uniwersytet Wrocławski)
Informacje podstawowe
Główny język publikacji
en
Czasopismo
Inorganic Chemistry
ISSN
0020-1669
EISSN
1520-510X
Wydawca
American Chemical Society
URL
Rok publikacji
2016
Numer zeszytu
4
Strony od-do
1758-1769
Numer tomu
55
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Język
eng
Treść
5,10,15,20-Tetraaryl-23-thiaazuliporphyrin (SAz) was synthesized starting from nonfunctionalized azulene using a U+0026amp;ldquo;1 + 3U+0026amp;rdquo; method to be applied as a monoanionic macrocyclic ligand that provides a peculiar [CNSN] coordination cavity. An insertion of palladium(II) afforded the cationic [PdII(SAz)]+, which readily undergoes the seven-membered ring contraction to form palladium(II) 23-thiabenzocarbaporphyrin [Pd(SBzC)] providing the first example of metal azuliporphyrinoid contraction. A reaction of SAz and a ruthenium source ([RuCl2(CO)3]2, [RuCl2(p-cymene)]2, or [RuCl2(cod)]) yielded ruthenium(II) 23-thiaazuliporphyrin [RuII(SAz)Cl(CO)]. As shown by X-ray crystallography the thiophene ring in [Ru(SAz)Cl(CO)] is sharply tilted out of the plane of the two pyrrole nitrogen and carbon atoms being bound to the ruthenium through the pyramidal sulfur in the U+0026amp;eta;1 fashion. In solution, as demonstrated by variable-temperature 1H NMR investigations, [Ru(SAz)Cl(CO)] exists as an equilibrium mixture of two isomers that are differentiated by the direction of thiophene folding (toward or outward of the axial chloride ligand). Apart of [RuII(SAz)Cl(CO)], ruthenium(III) 23-thiaazuliporphyrin [RuIII(SAz)Cl2] was obtained when [RuCl2(p-cymene)]2 or [RuCl2(cod)]n were used for insertion. The most characteristic 1H NMR features of paramagnetic [Ru(SAz)Cl2] are negative isotropic shifts of resonances assigned to meso-aryl, azulene, and pyrrolic hydrogen atoms. The analysis of contact shifts and the parallel density functional theory calculations of spin density distribution documented that in [Ru(SAz)Cl2] the metal ion acquires the dxy2(dxzdyz)3 ground electronic state. This Cs symmetry complex has singly occupied dxz or dyz orbitals that are symmetrically unequivalent. The resulting two different spin density distributions, when merged, reflect the spectroscopic image with the very specific U+0026amp;pi;-spin delocalization, also including the azulene moiety.
Cechy publikacji
original-article
Inne
System-identifier
2016CH7773
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