A Dirhoda‐Heterocyclic Carbene

Barnett, Harrison J.; Hill, Anthony F.

doi:10.1002/ange.201912650

Cited by 4 publications

(1 citation statement)

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“…Hence, it is desirable to establish a new rule governing the stabilities of metal carbido complexes. For binuclear metal carbido complexes containing a carbido bridge such as L n M = C = ML n and L n M ≡ C-M’L n , the central μ 2 -carbido ligand adopts an eight-electron configuration 4 , 5 . However, upon increasing the number of metals coordinated with the central single-carbon-atom ligand to three, the central μ 3 -carbido ligand does not always follow the eight-electron configuration 6 – 8 .…”

Section: Introductionmentioning

confidence: 99%

A stabilization rule for metal carbido cluster bearing μ3-carbido single-atom-ligand encapsulated in carbon cage

Guan,

Huang,

Xin

et al. 2024

Nat Commun

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Metal carbido complexes bearing single-carbon-atom ligand such as nitrogenase provide ideal models of adsorbed carbon atoms in heterogeneous catalysis. Trimetallic μ3-carbido clusterfullerenes found recently represent the simplest metal carbido complexes with the ligands being only carbon atoms, but only few are crystallographically characterized, and its formation prerequisite is unclear. Herein, we synthesize and isolate three vanadium-based μ3-CCFs featuring V = C double bonds and high valence state of V (+4), including VSc2C@Ih(7)-C80, VSc2C@D5h(6)-C80 and VSc2C@D3h(5)-C78. Based on a systematic theoretical study of all reported μ3-carbido clusterfullerenes, we further propose a supplemental Octet Rule, i.e., an eight-electron configuration of the μ3-carbido ligand is needed for stabilization of metal carbido clusters within μ3-carbido clusterfullerenes. Distinct from the classic Effective Atomic Number rule based on valence electron count of metal proposed in the 1920s, this rule counts the valence electrons of the single-carbon-atom ligand, and offers a general rule governing the stabilities of μ3-carbido clusterfullerenes.

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Section: Introductionmentioning

confidence: 99%

A stabilization rule for metal carbido cluster bearing μ3-carbido single-atom-ligand encapsulated in carbon cage

Guan,

Huang,

Xin

et al. 2024

Nat Commun

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Advances in Transition Metal Seleno‐ and Tellurocarbonyl Chemistry

Frogley

Hill

Watson

2020

Chemistry A European J

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In contrastt ot he ubiquity of transition-metal carbonyl, and (to al esser extent) thiocarbonyl complexes,t ransition-metal complexes of carbon monoselenide L n MCSe and monotellurideL n MCTer emain scarce. The last few years, however,h ave seen notable steps towards expanding this chemistry,specifically with regards to new systematic studies on homologous sets of chalcocarbonyl complexes L n MCE (E = O, S, Se, Te), the first reports of new bi-and polynuclear CSe and CTeb ridging complexesa nd ac onfluence with metal carbidoc hemistry.H erein the properties, syntheses and reactions of these rare but fundamentally intriguing compounds are discussed.

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Four‐Membered Bimetallic Carbon Complex [(M(η⁵‐C₅(CH₃)₅))₂(μ‐NPh)(μ‐C)] (M=Fe, Ru, Os) – An Ambiphilic Carbene with Lone Pair and σ‐Hole Reactivity

Parvathy

Parameswaran

2023

Chemistry A European J

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Singlet carbenes are extensively studied compounds capable of electrophilic, nucleophilic or ambiphilic behaviour. The ambiphilic reactivity of singlet carbenes has been conventionally observed in orthogonal planes. Here, we report a detailed bonding and reactivity study of a homobimetallic carbon complex [(MCp*)2(μ‐NPh)(μ‐C)] (1M, M=Fe, Ru, Os) that shows ambiphilicity in the same direction. The structure of this complex can be considered as two fused three‐membered M−C−M and M−N−M rings. The bonding analysis suggests that these 17 valence electron homobimetallic complexes have one formal M−M bond with a bridging carbene centre featuring a high‐lying spn‐hybridised lone pair. Accordingly, the carbene centre shows high proton affinity and act as a good 2e− donor to Lewis acids and transition metal fragment. Apart from the transition metal non‐bonding electrons, the π‐framework of M−C−M and M−N−M arms can be best described as 3c–2e− bonds. The two transition metals in the four‐membered skeleton generate many low‐lying, virtual orbitals. These low‐lying virtual orbitals induce electron excitation from the spn‐hybrid orbital in presence of H− and other 2e− donor ligands such as PMe3, NHC and CO. Hence, the spn‐hybrid lone pair orbital shows σ‐hole reactivity in presence of Lewis bases.

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A Dirhoda‐Heterocyclic Carbene

Cited by 4 publications

References 53 publications

A stabilization rule for metal carbido cluster bearing μ3-carbido single-atom-ligand encapsulated in carbon cage

A stabilization rule for metal carbido cluster bearing μ3-carbido single-atom-ligand encapsulated in carbon cage

Advances in Transition Metal Seleno‐ and Tellurocarbonyl Chemistry

Four‐Membered Bimetallic Carbon Complex [(M(η⁵‐C₅(CH₃)₅))₂(μ‐NPh)(μ‐C)] (M=Fe, Ru, Os) – An Ambiphilic Carbene with Lone Pair and σ‐Hole Reactivity

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A Dirhoda‐Heterocyclic Carbene

Cited by 4 publications

References 53 publications

A stabilization rule for metal carbido cluster bearing μ3-carbido single-atom-ligand encapsulated in carbon cage

A stabilization rule for metal carbido cluster bearing μ3-carbido single-atom-ligand encapsulated in carbon cage

Advances in Transition Metal Seleno‐ and Tellurocarbonyl Chemistry

Four‐Membered Bimetallic Carbon Complex [(M(η5‐C5(CH3)5))2(μ‐NPh)(μ‐C)] (M=Fe, Ru, Os) – An Ambiphilic Carbene with Lone Pair and σ‐Hole Reactivity

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Four‐Membered Bimetallic Carbon Complex [(M(η⁵‐C₅(CH₃)₅))₂(μ‐NPh)(μ‐C)] (M=Fe, Ru, Os) – An Ambiphilic Carbene with Lone Pair and σ‐Hole Reactivity