Formation of an imidazoliumyl-substituted [(LC )4 P4 ]4+ tetracation and transition metal mediated fragmentation and insertion reaction (LC = NHC)

Chemical Science
Kai SchwedtmannJan J Weigand

Abstract

Tetracationic cyclo-tetraphosphane [(LC)4P4]4+ as triflate salt (3[OTf]4) (LC = 4,5-dimethyl-1,3-diisopropyl-imidazol-2-yl) is obtained in high yield from the reduction of [LCPCl2]+ (4[OTf]) with 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine (6) and represents the first salt of the cationic cyclo-phosphane series with the general formula [L n P n ] n+. Theoretical calculations reveal the electrophilic nature of the P atoms within the P4-ring due to the influence of the imidazoliumyl-substituents. Further reduction of 3[OTf]4 with 6 affords the unexpected formation of the notricyclane P7-type cation [(LC)3P7]3+ (9[OTf]3). Selective transition metal mediated [2 + 2]-fragmentation of 34+ is achieved when 3[OTf]4 is reacted with Fe2(CO)9, Pd(PPh3)4 and Pt(PPh3)4 leading to the formation of the dicationic diphosphene complexes [(η2-LCP[double bond, length as m-dash]PLC)Fe(CO)4]2+ (12[OTf]2) and [(η2-LCP[double bond, length as m-dash]PLC)M(PPh3)2]2+ (13[OTf]2 for M = Pd; 14[OTf]2 for M = Pt). In contrast, the reaction of 3[OTf]4 with an excess of AuCl(tht) gives rise to the formation of the five-membered ring complex [((LC)4P4)AuCl2]3+ (15[OTf]3), where the Au(i) atom reductively inserts into a P-P bond of 34+.

References

Dec 2, 2004·Journal of the American Chemical Society·G K Surya PrakashGeorge A Olah
Apr 19, 2005·Chemical Communications : Chem Comm·Bobby D EllisCharles L B Macdonald
Aug 3, 2005·Chemistry : a European Journal·Ian P GrayJ Derek Woollins
Dec 17, 2005·Dalton Transactions : an International Journal of Inorganic Chemistry·Robert J BakerRobert Wolf
Jan 27, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Robert WolfEvamarie Hey-Hawkins
May 24, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Sahrah ParveenJ Derek Woollins
May 23, 2007·Journal of the American Chemical Society·C Adam DykerAndreas Decken
Dec 7, 2007·Dalton Transactions : an International Journal of Inorganic Chemistry·Santiago Gómez-Ruiz, Evamarie Hey-Hawkins
Jan 1, 2008·Chemistry : a European Journal·Douglas A Klumpp
Feb 4, 2010·Chemical Communications : Chem Comm·Stephen J Geier, Douglas W Stephan
Mar 24, 2010·Chemical Communications : Chem Comm·Eamonn ConradMichael J Ferguson
Sep 8, 2010·Inorganic Chemistry·Leslie D FieldPeter Turner
Nov 4, 2010·Journal of the American Chemical Society·Jan J WeigandFlorian D Henne
Jun 4, 2014·Chemistry : a European Journal·Manuel Alcarazo
Oct 22, 2014·Chemistry : a European Journal·Maximilian DonathJan J Weigand
Feb 17, 2015·Physical Chemistry Chemical Physics : PCCP·Shamil K LatypovOleg G Sinyashin
Sep 1, 2015·Angewandte Chemie·Jonathan H BarnardCaleb D Martin
Sep 25, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Andreas BeilHansjörg Grützmacher
Dec 2, 2015·Chemical Communications : Chem Comm·Florian D HenneJan J Weigand
Dec 3, 2015·Chemical Communications : Chem Comm·Kai SchwedtmannJan J Weigand
Jan 9, 2016·Journal of the American Chemical Society·Hiroyuki KawaiF Dean Toste
Feb 9, 2016·Chemical Society Reviews·Maximilian DonathJan J Weigand
Aug 17, 2016·Accounts of Chemical Research·Manuel Alcarazo
Nov 16, 2017·Chemistry : a European Journal·Justin F BinderCharles L B Macdonald
Mar 25, 2018·Chemistry, an Asian Journal·Kai SchwedtmannJan J Weigand

❮ Previous
Next ❯

Citations

Sep 29, 2019·Angewandte Chemie·Anup K AdhikariRobert Wolf
Aug 5, 2020·Chemical Communications : Chem Comm·Ravi YadavPeter W Roesky
Jun 20, 2020·Chemistry : a European Journal·Robin SchoemakerJan J Weigand
Mar 20, 2020·Chemical Science·Robin SchoemakerJan J Weigand
May 29, 2020·Angewandte Chemie·Helena BrakeManfred Scheer
Dec 21, 2019·Journal of the American Chemical Society·Ravi YadavPeter W Roesky

❮ Previous
Next ❯

Methods Mentioned

BETA
X-ray
NMR

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.