Mapa strony Przejdź do treści

Repozytorium

Wyszukaj

Kolekcje

Inne

Ruthenium(II) and ruthenium(III) complexes of p-benziporphyrin: merging equatorial and axial organometallic coordination.

Autorzy

Aneta Idec

Miłosz Pawlicki

Lechosław Latos-Grażyński

Rok wydania

2017

Czasopismo

Inorganic Chemistry

Numer woluminu

56

Strony

10337-10352

DOI

10.1021/acs.inorgchem.7b01237

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

A diamagnetic ruthenium(II) complex of 5,10,15,20-tetraphenyl-p-benziporphyrin [RuII(p-BzP)(CO)Cl] was obtained via the insertion of ruthenium into p-benziporphyrin using triruthenium(0) dodecacarbonyl [Ru3(CO)12] as the metal source. The procedure applying dichloro(cycloocta-1,5-diene)ruthenium(II) (polymer, [Ru(COD)Cl2]n) afforded the paramagnetic six-coordinate ruthenium(III) p-benziporphyrin [RuIII(p-BzP)Cl2]. As shown by X-ray crystallography, the p-phenylene ring in both complexes is sharply tilted out of the N3 plane, as reflected by the respective N3 (pyrrole)-C6 (p-phenylene) dihedral angle [RuII(p-BzP)(CO)Cl, 52.5°; RuIII(p-BzP)Cl2, 53.7°]. p-Phenylene is bound to the ruthenium cation in an η2 fashion, revealing the shortest ever Ru-C distance in the series of p-benziporphyrin complexes [RuII(p-BzP)(CO)Cl, 2.275(2) Å; RuIII(p-BzP)Cl2, 2.324(5) Å]. The reaction of RuII(p-BzP)(CO)Cl with ArMgCl or AlkMgCl results in the formation of diamagnetic six-coordinate ruthenium(II) p-benziporphyrin complexes containing the apically coordinated σ-alkyl or σ-aryl ligands, where the metal ion simultaneously coordinates to three carbon centers respectively accommodating η2 (phenylene) and σ (aryl and alkyl) modes. Reactions of σ-aryl (alkyl) carbanions with paramagnetic RuIII(p-BzP)Cl2 have been followed by 1H NMR spectroscopy. The procedure afforded the six-coordinate paramagnetic ruthenium(III) p-benziporphyrin [RuIII(p-BzP)(Ph)Cl], which binds one σ-aryl ligand, as reflected by the characteristic 1H NMR spectra spread within the +120 to -120 ppm range. Both paramagnetic complexes RuIII(p-BzP)(Ph)Cl and RuIII(p-BzP)(p-Tol)Cl are formed as a mixture of two stereoisomers differentiated by two nonequivalent locations of σ-aryl with respect to the puckered macrocyclic ring. The paramagnetic shifts of σ-aryls are indicative of π-spin delocalization patterns. Analysis of the contact shifts and parallel density functional theory calculations of the spin density distribution in RuIII(p-BzP)Cl2, RuIII(p-BzP)(Ar)Cl, and RuIII(p-BzP)(Alk)Cl reflect the features of the dxy2(dxzdyz)3 electronic ground state.

Adres publiczny

http://dx.doi.org/10.1021/acs.inorgchem.7b01237

Strona internetowa wydawcy

https://www.acs.org/content/acs/en.html

Podobne publikacje
2014

Merging of inner and outer ruthenium organometallic coordination motifs within an azuliporphyrin framework.

Białek Michał J., Latos-Grażyński Lechosław

2018

Incorporation of a p-phenylene unit into the azuliporphyrinogens frame-oxidation and ruthenium cluster coordination.

Sprutta Natasza, Hassa Agnieszka, Białek Michał J., Kodź-Wichowska Karolina, Kupietz Kamil, Latos-Grażyński Lechosław

2016

Palladium(II), ruthenium(II), and ruthenium(III) complexes of 23-thiaazuliporphyrin: the case of coordination-induced contraction.

Białek Michał J., Latos-Grażyński Lechosław