Isolation of homoleptic dicationic tellurium and monocationic bismuth analogues of non-N-heterocyclic carbene derivatives

Deka, Rajesh, Sarkar, Arup, Butcher, Ray J., Junk, Peter C., Turner, David R., Deacon, Glen B., and Singh, Harkesh B. (2020) Isolation of homoleptic dicationic tellurium and monocationic bismuth analogues of non-N-heterocyclic carbene derivatives. Organometallics, 39 (2). pp. 334-343.

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Abstract

The first examples of Te analogues of non-N-heterocyclic carbene (non-NHC) derivatives, [(ppy)₂Te]·2ClO₄, [4]·2ClO₄, and [(ppy)₂Te]·2OTf, [5]·2OTf [where ppy = 2-(2'pyridyl)phenyl and Tf = O₂SCF₃] are reported by the metathesis reaction of diorganoiodotelluronium(IV) cation, [(ppy)₂TeI]·I₃, [3]·I₃, with AgClO₄ and AgOTf, respectively. The metathesis reaction of ppyTeCl₃, 6, with an excess of AgClO₄ resulted in the isolation of [ppyTe(μ-O)]₂·2ClO₄, [8]·2ClO₄. The reaction of triorganotelluronium(IV) cation [(ppy)₃Te]·Br, [10]Br, with K₂PdCl₄ afforded [(ppy)₂TeCl]·[(ppy)PdCl₂], 11. The generality of the "ppy" group on stabilizing other main-group non-NHC analogues has been further established by synthesizing the second example of a Bi analogue of a non-NHC derivative, namely, bismuthenium ion, [(ppy)₂Bi]·Cl, [12]·Cl, using the same aryl group. All of the synthesized compounds are unambiguously authenticated by single-crystal X-ray diffraction studies. DFT calculations [natural bond orbital (NBO), atoms in molecules (AIM), and electron localization function (ELF)] indicate that the stability of the non-NHC carbenoids relies on the a-hole participation of the Te/Bi atom with the strong intramolecular coordination ability of the pyridyl N atom of the aryl substituent.

Item ID: 62344
Item Type: Article (Research - C1)
ISSN: 1520-6041
Copyright Information: © 2020 American Chemical Society.
Funders: Department of Science and Technology of India (DST), IITB-Monash Research Academy (IITB-MRA)
Projects and Grants: DST J.C. Bose Fellowship 15DSTFLS002, Grant No. RD/0115-DSTFLS80-004, IITB-MRA IMURA 0242
Date Deposited: 26 Feb 2020 07:47
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030204 Main Group Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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