Highly Reactive Cyclic(alkyl)(amino) Carbene- and N-Heterocyclic Carbene-Bismuth(III) Complexes: Synthesis, Structure, and Computations

Inorganic Chemistry
Guocang WangRobert J Gilliard

Abstract

Cyclic(alkyl)(amino) carbene (CAAC)-stabilized complexes of phosphorus, one of the lightest group 15 elements, are well-established and can often be obtained in high yields. In contrast, analogous CAAC compounds of bismuth, the heaviest nonradioactive member of group 15, are unknown. Indeed, reactivity increases as you descend the group, and as a result there are only a few examples of N-heterocyclic carbene (NHC)-bismuth complexes. Moreover, activated bismuth compounds often readily extrude bismuth metal, making isolation of stable complexes highly challenging. We report that CAACs react with phenylbismuth dichloride (PhBiCl2) to afford Et2CAAC-Bi(Ph)Cl2 and CyCAAC-Bi(Ph)Cl2. Significantly, these complexes represent the first structurally characterized examples of CAAC-coordination to bismuth. The CAAC-stabilized bismuth compounds can also be obtained from air-stable salts, [Et2CAAC-H]22+ [Cl2(Ph)Bi(μ-Cl2)Bi(Ph)Cl2]2- and [CyCAAC-H]22+ [Cl2(Ph)Bi(μ-Cl2)Bi(Ph)Cl2]2-, by deprotonation with potassium bis(trimethylsilyl)amide, K[N(SiMe3)2]. The electronic effects of the ligand on the bismuth center were investigated by comparing the CAAC-Bi(Ph)Cl2 complexes to the NHC analogues, SIPr-Bi(Ph)Cl2(THF) and IPr-Bi(Ph)Cl2 (SIPr = 1,3-bi...Continue Reading

References

Sep 26, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Markus BrymDavid R Turner
Nov 26, 2009·Chemistry : a European Journal·Mariham Y AbrahamGregory H Robinson
Jun 4, 2011·Inorganic Chemistry·Yuzhong Wang, Gregory H Robinson
Jul 24, 2013·Chemical Science·Caleb D MartinGuy Bertrand
Sep 17, 2013·Chemistry : a European Journal·David J D Wilson, Jason L Dutton
Oct 24, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Antonino AprileJason L Dutton
Jun 27, 2014·Nature·Matthew N HopkinsonFrank Glorius
Oct 25, 2014·Inorganic Chemistry·Yuzhong Wang, Gregory H Robinson
Dec 18, 2014·Accounts of Chemical Research·Michèle Soleilhavoup, Guy Bertrand
Mar 2, 2016·Accounts of Chemical Research·Sudipta RoyHerbert W Roesky
Feb 24, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Blaž AličGašper Tavčar
Apr 5, 2017·Angewandte Chemie·Mohand MelaimiGuy Bertrand
Aug 3, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Jordan B WatersJose M Goicoechea
Nov 3, 2017·Chemical Communications : Chem Comm·Robert J GilliardJohn D Protasiewicz
Nov 9, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Adinarayana DoddiMatthias Tamm
Nov 10, 2017·Chemistry : a European Journal·Cameron M E GrahamPaul J Ragogna
Nov 21, 2017·Angewandte Chemie·Gabriele HierlmeierJose M Goicoechea
Jul 4, 2018·Chemical Reviews·Vitaly NesterovShigeyoshi Inoue

❮ Previous
Next ❯

Citations

Feb 2, 2019·Chemistry : a European Journal·Guocang WangRobert J Gilliard

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.

Related Papers

Chemical Communications : Chem Comm
Amit Pratap SinghAdam Lange
Dalton Transactions : an International Journal of Inorganic Chemistry
Steven P FisherVincent Lavallo
© 2022 Meta ULC. All rights reserved