Activation of carbon dioxide and carbon disulfide by a scandium N-heterocyclic carbene complex

Arnold, Polly L.; Marr, Isobel A.; Zlatogorsky, Sergey; Bellabarba, Ronan M.; Tooze, Robert P.

doi:10.1039/c3dt52762j

Cited by 58 publications

(31 citation statements)

References 31 publications

(48 reference statements)

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“…The solid‐state structures, shown in Figure , reveal that the alkoxy‐NHC ligand is bound to tantalum in a chelate (O,C) fashion in both species. The ligand C NHC ‐Ta‐O bite angles (75.69(16)° in 3 and 76.74(15)° in 4 ) are relatively tight for six‐membered metallacycles, but compare well with those reported in the literature for related early‐TM complexes . Both complexes adopt a pseudo‐square‐pyramidal geometry ( τ 5 =0.31 for 3 , τ 5 =0.09 for 4 ) with the tert ‐butylimido in 3 and the neopentylidene in 4 in the axial positions, and the alkoxy‐carbene and the two neopentyls in the square‐planar base.…”

Section: Resultssupporting

confidence: 78%

Early/Late Heterobimetallic Tantalum/Rhodium Species Assembled Through a Novel Bifunctional NHC‐OH Ligand

Srivastava

Moneuse

Petit

et al. 2018

Chemistry A European J

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The straightforward synthesis of a new unsymmetrical hydroxy-tethered N-heterocyclic carbene (NHC) ligand, HL, is presented. The free ligand exhibits an unusual OH-carbene hydrogen-bonding interaction. This OH-carbene motif was used to yield 1) the first tantalum complex displaying both a Fischer- and Schrock-type carbene ligand and 2) a unique NHC-based early/late heterobimetallic complex. More specifically, the protonolysis chemistry between the ligand's hydroxy group and imido-alkyl or alkylidene-alkyl tantalum precursor complexes yielded the rare monometallic tantalum-NHC complexes [Ta(XtBu)(L)(CH tBu) ] (X=N, CH), in which the alkoxy-carbene ligand acts as a chelate. In contrast, HL only binds to rhodium through the NHC unit in [Rh(HL)(cod)Cl] (cod=cycloocta-1,5-diene), the hydroxy pendant arm remaining unbound. This bifunctional ligand scaffold successfully promoted the assembly of rhodium/tantalum heterobimetallic complexes upon either 1) the insertion of [Rh(cod)Cl] into the Ta-NHC bond in [Ta(NtBu)(L)(CH tBu) ] or 2) protonolysis between the free hydroxy group in [Rh(HL)(cod)Cl] and one alkyl group in [Ta(NtBu)(CH tBu) ].

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Section: Resultssupporting

confidence: 78%

Early/Late Heterobimetallic Tantalum/Rhodium Species Assembled Through a Novel Bifunctional NHC‐OH Ligand

Srivastava

Moneuse

Petit

et al. 2018

Chemistry A European J

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“…[37] In 2011, Ajitha and Suresh assessed the influence of stereoelectronic factors on the CO 2 capture and fixation ability of NHCs using DFT modeling. [37] In 2011, Ajitha and Suresh assessed the influence of stereoelectronic factors on the CO 2 capture and fixation ability of NHCs using DFT modeling.…”

Section: Imidazolium Ils For Co 2 Photoreductionmentioning

confidence: 99%

Imidazolium Ionic Liquids, Imidazolylidene Heterocyclic Carbenes, and Zeolitic Imidazolate Frameworks for CO₂ Capture and Photochemical Reduction

2015

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Imidazolium ionic liquids (ILs), imidazolylidene N-heterocyclic carbenes (NHCs), and zeolitic imidazolate frameworks (ZIFs) are imidazolate motifs which have been extensively investigated for CO2 adsorption and conversion applications. Summarized in this minireview is the recent progress in the capture, activation, and photochemical reduction of CO2 with these three imidazolate building blocks, from homogeneous molecular entities (ILs and NHCs) to heterogeneous crystalline scaffolds (ZIFs). The developments and existing shortcomings of the imidazolate motifs for their use in CO2 utilizations is assessed, with more of focus on CO2 photoredox catalysis. The opportunities and challenges of imidazolate scaffolds for future advancement of CO2 photochemical conversion for artificial photosynthesis are discussed.

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“…Accordingly, these tethered NHC ligands can function as reactive ligands, and the combination of the Lewis acidic metal cation and nucleophilic carbene ligand has led us to compare the reactivity of these complexes to frustrated Lewis pairs. 32,33 For example, we have shown that polar substrates can be cleaved heterolytically, in a reversible manner, across the metal-NHC bond. Subsequent heating of these addition products led to an elimination of the functionalised substrate from the lanthanide complex, reforming the metalcarbene bond.…”

Section: Introductionmentioning

confidence: 99%

Homo- and heteroleptic alkoxycarbene f-element complexes and their reactivity towards acidic N–H and C–H bonds

et al. 2014

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The reactivity of a series of organometallic rare earth and actinide complexes with hemilabile NHC-ligands towards substrates with acidic C-H and N-H bonds is described. The synthesis, characterisation and X-ray structures of the new heteroleptic mono- and bis(NHC) cyclopentadienyl complexes LnCp2(L) 1 (Ln = Sc, Y, Ce; L = alkoxy-tethered carbene [OCMe2CH2(1-C{NCHCHN(i)Pr})]), LnCp(L)2 (Ln = Y) , and the homoleptic tetrakis(NHC) complex Th(L)4 4 are described. The reactivity of these complexes, and of the homoleptic complexes Ln(L)3 (Ln = Sc 3, Ce), with E-H substrates is described, where EH = pyrrole C4H4NH, indole C8H6NH, diphenylacetone Ph2CC(O)Me, terminal alkynes RC≡CH (R = Me3Si, Ph), and cyclopentadiene C5H6. Complex 1-Y heterolytically cleaves and adds pyrrole and indole N-H across the metal carbene bond, whereas 1-Ce does not, although 3 and 4 form H-bonded adducts. Complexes 1-Y and 1-Sc form adducts with CpH without cleaving the acidic C-H bond, 1-Ce cleaves the Cp-H bond, but 2 reacts to form the very rare H(+)-[C5H5](-)-H(+) motif. Complex 1-Ce cleaves alkyne C-H bonds but the products rearrange upon formation, while complex 1-Y cleaves the C-H bond in diphenylacetone forming a product which rearranges to the Y-O bonded enolate product.

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Activation of carbon dioxide and carbon disulfide by a scandium N-heterocyclic carbene complex

Cited by 58 publications

References 31 publications

Early/Late Heterobimetallic Tantalum/Rhodium Species Assembled Through a Novel Bifunctional NHC‐OH Ligand

Early/Late Heterobimetallic Tantalum/Rhodium Species Assembled Through a Novel Bifunctional NHC‐OH Ligand

Imidazolium Ionic Liquids, Imidazolylidene Heterocyclic Carbenes, and Zeolitic Imidazolate Frameworks for CO₂ Capture and Photochemical Reduction

Homo- and heteroleptic alkoxycarbene f-element complexes and their reactivity towards acidic N–H and C–H bonds

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Activation of carbon dioxide and carbon disulfide by a scandium N-heterocyclic carbene complex

Cited by 58 publications

References 31 publications

Early/Late Heterobimetallic Tantalum/Rhodium Species Assembled Through a Novel Bifunctional NHC‐OH Ligand

Early/Late Heterobimetallic Tantalum/Rhodium Species Assembled Through a Novel Bifunctional NHC‐OH Ligand

Imidazolium Ionic Liquids, Imidazolylidene Heterocyclic Carbenes, and Zeolitic Imidazolate Frameworks for CO2 Capture and Photochemical Reduction

Homo- and heteroleptic alkoxycarbene f-element complexes and their reactivity towards acidic N–H and C–H bonds

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Imidazolium Ionic Liquids, Imidazolylidene Heterocyclic Carbenes, and Zeolitic Imidazolate Frameworks for CO₂ Capture and Photochemical Reduction