Isolation of homoleptic dicationic tellurium and monocationic bismuth analogues of non-N-heterocyclic carbene derivatives
Journal Publication ResearchOnline@JCUAbstract
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.
Journal
Organometallics
Publication Name
N/A
Volume
39
ISBN/ISSN
1520-6041
Edition
N/A
Issue
2
Pages Count
10
Location
N/A
Publisher
American Chemical Society
Publisher Url
N/A
Publisher Location
N/A
Publish Date
N/A
Url
N/A
Date
N/A
EISSN
N/A
DOI
10.1021/acs.organomet.9b00698