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NHCs as ligands are known for their strong σ donation and high structural tunability. [11] More in-depth computational analyses also highlight the role of M to NHC π back-donation, with respect to a description of an M-NHC bond. [12] Contour line diagrams of the Laplacian distribution of three (NHC)MCl complexes.
In coordination chemistry, a transition metal NHC complex is a metal complex containing one or more N-heterocyclic carbene ligands. Such compounds are the subject of much research, in part because of prospective applications in homogeneous catalysis. One such success is the second generation Grubbs catalyst. [1] IMes is a popular NHC ligand.
This effect can be used to stabilize highly reactive main group and transition metal compounds. [6] [22] Because excessive steric hindrance can be an issue for some reactivity, NHCs and CAACs bearing substituents with multiple spatial conformations (e.g. cyclohexyl) offer "flexible steric bulk" for catalysis.
The transmetallated NHCs can either be isolated for subsequent reaction with palladium in a two-step method, or generated in the presence of palladium in a one-pot reaction. However, generation of Pd-NHC complexes by Ag transmetallation is cost-prohibitive and hampered by Ag complexes’ light sensitivity.
When deprotonated, NHOs can be ligands for main group hydrides. E = Ge, Sn. [1] NHOs can stabilize low oxidation state main group hydrides, like GeH 2 and SnH 2 that are coordinated to W(CO) 5. [1] When deprotonated, these NHOs become anionic, four-electron bridging ligands that can bind to two Ge centers, hence displaying carbanion-like ...
Smaller substituents may be cleaved. Direct metalation by silver(I) with imidazolium salts can cause cleavage at the C2 position if methyl is used as the blocking group. The result is formation of normal NHC carbenes. n-alkyl and benzyl groups may undergo the same fate as the methyl group. Steric bulk may also influence the formation of MIC ...
One quintessential dinitrogen complex of a main group element is Gernot Frenking’s triphenylphosphinazine, first reported in 2013 in Angewandte Communications. [6] This compound was notable for demonstrating the double Lewis acid behavior of dinitrogen, as the publication describes the N 2 moiety in the doubly excited 1 Γ g state with four lone pairs on N—N fragment.
A transition metal carbene complex is an organometallic compound featuring a divalent carbon ligand, itself also called a carbene. [1] Carbene complexes have been synthesized from most transition metals and f-block metals, [2] using many different synthetic routes such as nucleophilic addition and alpha-hydrogen abstraction. [1]