Synthesis and Reactivity of Heteroleptic Ga-P-C Allyl Cation Analogues
Bin Li1, Christoph Wölper1, Gebhard Haberhauer2
1Institute of Inorganic Chemistry and Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen, Universitätsstrasse 5-7, 45141, Essen, Germany.
Abstract:
Oxidative addition of cyclic alkyl(amino)carbene-coordinated phosphinidenes (Me cAAC)PX to LGa affords gallium-coordinated phosphinidenes LGa(X)-P(Me cAAC) (L=HC[C(Me)N(2,6-i-Pr2 C6 H3 )]2 ; X=Cl 1, Br 2), which react with NaBArF 4 and LiAl(ORF )4 to [LGaP(Me cAAC)][An] (An=B(C6 H3 (CF3 )2 )4 3, B(C6 F5 )4 4, Al(OC(CF3 )3 )4 5). The cations in 3-5 show substantial Ga-P double bond character and represent heteronuclear analogues of allyl cations according to quantum chemical calculations. The reaction of 4 with 4-dimethylaminopyridine (dmap) to adduct 6 confirms the strong electrophilic nature of the gallium center, whereas 5 reacts with ethyl isocyanate with C-C bond formation to the γ-C atom of the β-diketiminate ligand and formation of compound 7.
More Related Videos
10:42Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
07:50Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
Published on: May 26, 2019
Related Concept Videos
π Molecular Orbitals of the Allyl Cation and Anion
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
Electrophilic Addition to Alkynes: Halogenation
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Acid Halides to Ketones: Gilman Reagent
As shown below, the mechanism proceeds in two steps. First, one of the alkyl groups of the reagent acts as a nucleophile and attacks the acyl carbon of the acid chloride to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen...
Cycloaddition Reactions: Overview
