title: Bismuthπ arene versus bismuthhalide coordination in heterocyclic diorganobismuth(iii) compounds with transannular N→Bi interaction.
abstract: New diorganobismuth(iii) bromides of type [RN(CH2C6H4)2]BiBr [R = C6H5CH2(1), C6H5CH2CH2(2), and CH3OCH2CH2(3)], based on the heterocyclic butterfly-like tetrahydro-dibenzo[c,f][1,5]azabismocine framework, were prepared starting from the corresponding RN(CH2C6H4Br-2)2in a succession of reactions including ortho-lithiation and treatment of the dilithio derivative with BiBr3in a 1 : 1 molar ratio. Further exchange reactions between bromides and appropriate metal halides or ammonium fluoride resulted in the formation of [RN(CH2C6H4)2]BiX [X = Cl and I for R = C6H5CH2(4 and 5) and C6H5CH2CH2(6 and 7) and X = F (8), Cl (9), and I (10) for R = CH3OCH2CH2]. All ten compounds were structurally characterized in solution by NMR and in the solid state by single-crystal X-ray diffraction. Strong transannular N→Bi interactions were observed in all the investigated diorganobismuth(iii) halides, thus giving rise to hypervalent 10-Bi-4 species in 1, 2, 4-7 and 12-Bi-5 species in 3, 8-10, where the oxygen atom in the pendant arm is intramolecularly coordinated to bismuth. The molecules are associated in dimeric units by strong Biπ arene interactions in 3, 4, and 10 (approx. 3.50 Å) and by BiX interactions in 1, 5, and 7. Bromide 1, chloride 4, and iodide 5 are isostructural, but stronger polarization of the Bi-Cl bond favors Biπ arene interaction in 4 over Bihalide interactions, as observed in 1 and 5. In the isostructural series [RN(CH2C6H4)2]BiX (R = CH3OCH2CH2), Bioxygen interactions compensate the electron deficiency at bismuth in fluoride 8 and chloride 9, whereas the coordination sphere of bismuth is completed by a combination of Biπ arene and Bihalide interactions in bromide 3 and only by Biπ arene interactions in iodide 10. Moreover, weak Hπ arene and HX intermolecular interactions, mainly of dispersion type, contribute to supramolecular networks in all three series of compounds.
authors.affiliation: Supramolecular Organic and Organometallic Chemistry Centre, Faculty of Chemistry & Chemical Engineering, Chemistry Department, Babes-Bolyai University, RO-400028 Cluj-Napoca, Romania. ancas@chem.ubbcluj.ro.
authors.forename: Ana Maria
authors.initials: AM
authors.lastname: Toma
authors.affiliation: Supramolecular Organic and Organometallic Chemistry Centre, Faculty of Chemistry & Chemical Engineering, Chemistry Department, Babes-Bolyai University, RO-400028 Cluj-Napoca, Romania. ancas@chem.ubbcluj.ro.
authors.forename: Alexandra
authors.initials: A
authors.lastname: Pop
authors.affiliation: Supramolecular Organic and Organometallic Chemistry Centre, Faculty of Chemistry & Chemical Engineering, Chemistry Department, Babes-Bolyai University, RO-400028 Cluj-Napoca, Romania. ancas@chem.ubbcluj.ro.
authors.forename: Anca
authors.identifier: http://orcid.org/0000-0002-0942-581X
authors.initials: A
authors.lastname: Silvestru
authors.affiliation: Technische Universität Chemnitz, Institut für Chemie, Anorganische Chemie, D-09107 Chemnitz, Germany. heinrich.lang@chemie.tu-chemnitz.de.
authors.forename: Tobias
authors.identifier: http://orcid.org/0000-0001-8948-1477
authors.initials: T
authors.lastname: Rüffer
authors.affiliation: Technische Universität Chemnitz, Institut für Chemie, Anorganische Chemie, D-09107 Chemnitz, Germany. heinrich.lang@chemie.tu-chemnitz.de.
authors.forename: Heinrich
authors.initials: H
authors.lastname: Lang
authors.affiliation: Technische Universität Chemnitz, Institut für Chemie, Koordinationschemie, D-09107 Chemnitz, Germany. michael.mehring@chemie.tu-chemnitz.de.
authors.forename: Michael
authors.initials: M
authors.lastname: Mehring