title: Fusion and Desulfurization Reactions of Thiomorpholinochlorins.
abstract: An unusually nonplanar, ruffled structure that had been suspected for the previously reported [2,3-bismethylenethiomorpholinochlorinato]nickel(II) complex was confirmed by determination of its crystal structure. Treatment of this thiomorpholinochlorin with acid converts the exocyclic double bonds to direct links to the ortho-positions of both adjacent meso-phenyl groups. The crystal structure of this product indicated that the introduction of these linkages did not change the overall conformation of the macrocycle. The reactivity of the bis-linked thiomorpholine moiety with respect to Raney-nickel-induced (hydro)desulfurization reactions was probed, forming a bis-phenyl-linked 2,3-dimethylchlorin, also characterized by X-ray diffraction, and a bis-indene-annulated porphyrin. We also report on the synthesis of the oxygen analogue to the bis-linked thiomorpholine by reaction of a secochlorin bisketone nickel complex with Woollins' reagent. We thus introduce novel methodologies toward the synthesis of porphyrinoids carrying β-to-ortho-phenyl fusions and expand on the scope and limits of the chemistry and interconversion of pyrrole-modified porphyrins.
authors.affiliation: Department of Chemistry, University of Connecticut , Unit 3060, Storrs, Connecticut 06269-3060, United States.
authors.forename: Meenakshi
authors.initials: M
authors.lastname: Sharma
authors.affiliation: Department of Chemistry, University of Connecticut , Unit 3060, Storrs, Connecticut 06269-3060, United States.
authors.forename: Subhadeep
authors.initials: S
authors.lastname: Banerjee
authors.affiliation: Department of Chemistry, Purdue University , 560 Oval Drive, West Lafayette, Indiana 47907-2084, United States.
authors.forename: Matthias
authors.initials: M
authors.lastname: Zeller
authors.affiliation: Department of Chemistry, University of Connecticut , Unit 3060, Storrs, Connecticut 06269-3060, United States.
authors.forename: Christian
authors.identifier: 0000-0002-1560-7345
authors.initials: C
authors.lastname: Brückner