title: Synthesis, characterization, and ligand behaviour of a new ditelluroether (C10H7)Te(CH2)4Te(C10H7) and the concurrently formed ionic [(C10H7)Te(CH2)4]Br.
abstract: The reaction of 1-naphthyl bromide with n-butyl lithium, elemental tellurium, and 1,4-dibromobutane in THF affords both (C10H7)Te(CH2)4Te(C10H7) (1) and [(C10H7)Te(CH2)4]Br (2) in good yields. 1 is preferentially formed at low temperatures and is a rare example of a structurally characterized ditelluroether in which the tellurium atoms are bridged by a hydrocarbon chain. In the solid state, 1 shows secondary bonding TeTe interactions, which connect the molecules into layers which are further linked to 3-dimensional frameworks by TeH hydrogen bonds. [(C10H7)Te(CH2)4]Br (2) is formed concurrently during the synthesis of 1 and is the main product, when the reaction is carried out at room temperature. The revPBE/def2-TZVPP calculations of the reaction profiles indicate that the formation of 2 is somewhat more favourable than that of 1. Furthermore, at room temperature the activation energy for the formation of 2 is lower than that of 1. At low temperatures the activation energy of the reaction leading to 1 is lower than that to 2, which is consistent with the synthetic observations. When 1 was treated with CuBr, [Cu2(μ-Br)2{μ-(C10H7)Te(CH2)4Te(C10H7)}2] (3) was formed. It crystallizes as two polymorphs (3a) and (3b) in which both the packing and the conformation of the ditelluroether ligands are different. The reaction of 1 with HgCl2produces [(C10H7)Te(CH2)4]2[HgCl4]·CH2Cl2(4·CH2Cl2) and that of 1 with CuCl2affords [(C10H7)Te(CH2)4]Cl (5). 2 and 5 are isomorphous.
authors.affiliation: Laboratory of Inorganic Chemistry, University of Oulu, P. O. Box 3000, FI-90014 Oulu, Finland. risto.laitinen@oulu.fi.
authors.forename: Merja J
authors.initials: MJ
authors.lastname: Poropudas
authors.affiliation: Laboratory of Inorganic Chemistry, University of Oulu, P. O. Box 3000, FI-90014 Oulu, Finland. risto.laitinen@oulu.fi.
authors.forename: J Mikko
authors.identifier: http://orcid.org/0000-0002-3695-4151
authors.initials: JM
authors.lastname: Rautiainen
authors.affiliation: Laboratory of Inorganic Chemistry, University of Oulu, P. O. Box 3000, FI-90014 Oulu, Finland. risto.laitinen@oulu.fi.
authors.forename: Raija
authors.initials: R
authors.lastname: Oilunkaniemi
authors.affiliation: Laboratory of Inorganic Chemistry, University of Oulu, P. O. Box 3000, FI-90014 Oulu, Finland. risto.laitinen@oulu.fi.
authors.forename: Risto S
authors.initials: RS
authors.lastname: Laitinen