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Ruthenium(II) and Ruthenium(III) Complexes of p-Benziporphyrin: Merging Equatorial and Axial Organometallic Coordination.

Inorganic Chemistry 2017 September 6
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 by1 H 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 characteristic1 H 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 dxy 2 (dxz dyz )3 electronic ground state.

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