Journal ArticleDOI
Extending the chemistry of carbones: P–N bond cleavage via an SN2′-like mechanism
Chitra Gurnani,Nemanja Đorđević,Senthilkumar Muthaiah,Dušan Dimić,Rakesh Ganguly,Milena Petković,Dragoslav Vidovic +6 more
TLDR
The reactivity of nucleophilic carbodiphosphorane and carbodicarbene towards various dichlorophosphines has been explored and the use of MeN(PCl2)2 resulted in a unique P-N bond cleavage that, according to computational studies, occurred via an SN2'-like mechanism.About:
This article is published in Chemical Communications.The article was published on 2015-06-18. It has received 10 citations till now. The article focuses on the topics: Bond cleavage & SN2 reaction.read more
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Geminal Dianions Stabilized by Main Group Elements
TL;DR: In this review, the syntheses and electronic structures of the geminal dianions are presented, followed by the studies dedicated to their reactivity toward organic substrates and finally to their coordination chemistry and applications.
Journal ArticleDOI
Carbodicarbene Bismaalkene Cations: Unravelling the Complexities of Carbene versus Carbone in Heavy Pnictogen Chemistry.
Jacob E. Walley,Levi S. Warring,Guo-Cang Wang,Diane A. Dickie,Sudip Pan,Gernot Frenking,Robert J. Gilliard +6 more
TL;DR: The CDC ligand has a remarkable influence on the overall stability of the resulting low‐coordinate Bi complexes, suggesting that CDC is a superior ligand to NHC in heavy pnictogen chemistry.
Journal ArticleDOI
Bis(carbodicarbene)phosphenium trication: the case against hypervalency
TL;DR: The first example of a phosphenium trication has been prepared by using the exceptional nucleophilic properties of a carbodicarbene ligand and it is shown that phosphoranides, in general, do not contain a hypervalent P centre.
Journal ArticleDOI
Preparation, Structural Analysis, and Reactivity Studies of Phosphenium Dications
Madelyn Qin Yi Tay,Gordana Ilić,Ulrike Werner-Zwanziger,Yunpeng Lu,Rakesh Ganguly,Louis Ricard,Gilles Frison,Duncan Carmichael,Dragoslav Vidovic +8 more
TL;DR: In this paper, the synthesis and reactivity of the two-coordinate P(III)-containing dication [((Ph3P)2C)P(NiPr2)]2+ (3a2+) have been investigated.
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Hexaphenyl carbodiphosphorane adducts of heavier group 15 element trichlorides: syntheses, properties and reactivities.
TL;DR: Additional reactivity studies revealed an intramolecular electrophilic aromatic substitution (SEAr) in 1+, which represents an excellent starting point for further selective C-P bond formation reactions.
References
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Synthesis of an Extremely Bent Acyclic Allene (A “Carbodicarbene”): A Strong Donor Ligand
TL;DR: It is reasoned that weakening the p bonds of all-carbon allenes A1 should make them more flexible, and ultimately lead to a bending of the otherwise rigid and linear C=C=C skeleton, and it is shown that bent allenes should not be considered as laboratory curiosities, but instead a novel class of strong h-donor ligands for transition-metal centers.
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Nucleophilic and organometallic displacement reactions of allylic compounds: stereo-and regiochemistry
TL;DR: In this paper, stereo and regiochemical aspects of three reaction types: the SN2' reaction (bimolecular nucleophilic substitution with allylic rearrangement); displacement reactions effected by organometallic reagents; the conversion of allylic alcohols into halides.
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Divalent Carbon(0) Chemistry, Part 1: Parent Compounds
Ralf Tonner,Gernot Frenking +1 more
TL;DR: The results show that the bonding situations in L(2)C compounds 1-8 can be interpreted in terms of donor-acceptor interactions between closed-shell ligands L and a carbon atom which has two lone-pair orbitals L-->C<--L, and particularly for the carbodiphosphoranes 1-3, which are classified as divalent carbon(0) compounds.
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C(NHC)2: divalent carbon(0) compounds with N-heterocyclic carbene ligands-theoretical evidence for a class of molecules with promising chemical properties.
Ralf Tonner,Gernot Frenking +1 more