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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.
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.
Ever since the first crystalline carbene structure was isolated by Arduengo ins 1990, tuning different properties of NHCs has been a popular area of study in main group chemistry. [4] The first NHC boryl anion was synthesized by Segawa in 2006. [1]
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 ...
Most homoleptic organo-main group compounds adopt a characteristic oxidation state: RLi, R 2 Be, R 3 B/R 3 Al, R 4 Si, R 3 P, R 2 S. Members where the simplest stoichiometry violates the octet rule often aggregate by formation of bridging alkyl groups. When the alkyl group bridges two main group elements, the bonding is called three-center two ...
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]
Adding "steric hindrance" to a molecule's reactive site through bulky groups is a common strategy in molecular chemistry to stabilize reactive moieties within a molecule. [3] In this case bulky ligands like terphenyls, bulky alkoxides, aryl-substituted NHCs, etc. serve as a protective wrapper on the molecule. [1]
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.