[2-{E(CH2CH2)2NCH2}C6H4]nBiX3-n (E = O, NMe; X = Cl, Br, I; n = 1-3) and [2-(Me2NCH2)C6H4]BiBr2 - new hypervalent organobismuth(III) compounds

Hans J. Breunig (1) , Mihai G. Nema (2) , Cristian Silvestru (3) , Albert Soran (2) , Richard A. Varga (2)

1 Institut für Anorganische und Physikalische Chemie
2 Faculty of Chemistry and Chemical Engineering
3 Faculty of Chemistry and Chemical Engineering

The homoleptic [2-{E(CH2CH2)2NCH2}C6H4]3Bi [E = O (1), MeN (2)], the chlorides [2-{E(CH2CH2)2NCH2}C6H4]2BiCl [E = O (3), MeN (4)] and the dichloride [2-{E(CH2CH2)2NCH2}C6H4]BiCl2 [E = O (5), MeN (6)] have been synthesized by reacting the corresponding ortho-lithium derivative with BiCl3 in corresponding molar ratios. The dihalides [2-{E(CH2CH2)2NCH2}C6H4]BiX2 [X = Br, E = O (7), MeN (9); X = I, E = O (8), MeN (10)] as well as [2-(Me2NCH2)C6H4]BiBr2 (11) were obtained by halide exchange reactions between RBiCl2 and excess aqueous solution of KX. The compounds were characterized by multinuclear (1H, 13C) NMR and MS. The crystal and molecular structures of 1-5 and 11 were determined by single-crystal X-ray diffraction. In all compounds the (C6H4CH2)N atoms are coordinated to Bi. The crystals of 1 and 2, as well as those of the chlorides 3 and 4, contain discrete molecules. For R3Bi intramolecular N→Bi interactions of medium strength [Bi(1)-N(1) 3.170(7) Å for 1 and 3.211(5) Å for 2] result in an overall distorted octahedral (C,N)3Bi core. In the monochlorides one nitrogen is strongly coordinated to Bi [2.660(11) Å for 3 and 2.744(14) Å for 4] trans to the halogen, while the second one is involved in a weaker intramolecular N→Bi interaction [3.095(11) Å for 3 and 3.061(14) Å for 4] trans to a carbon atom. The overall (C,N)2BiCl core is distorted square-pyramidal. The crystals of the monohalides 5 and 11 contain discrete dimer units. The pendant arm nitrogen atom is strongly coordinated [2.548(9) Å for 5 and 2.485(13) Å for 11] trans to the bridging halogen, thus resulting in an overall distorted square-pyramidal (C,N)BiX3 (X = Cl, Br) core. The six-membered morpholinyl and piperazinyl rings in 1-5 adopt the chair conformation which prevents intramolecular coordination of the O or N(Me) atoms to Bi. Supramolecular architectures based on intermolecular Bi∙∙∙Br interactions, Cl∙∙∙H and Br∙∙∙H contacts are formed in the crystals of 3, 5 and 11.

Mots clés: Physical Sciences

Hans J. Breunig, Mihai G. Nema, Cristian Silvestru, Albert Soran, Richard A. Varga. [2-{E(CH2CH2)2NCH2}C6H4]nBiX3-n (E = O, NMe; X = Cl, Br, I; n = 1-3) and [2-(Me2NCH2)C6H4]BiBr2 - new hypervalent organobismuth(III) compounds. Journal of Inorganic and General Chemistry / Zeitschrift für anorganische und allgemeine Chemie, 2010, 636 (13-14), pp.2378. ⟨10.1002/zaac.201000233⟩. ⟨hal-00599883⟩