Molecular Zinc Dihydride Stabilized by N‐Heterocyclic Carbenes

Rit, Arnab; Spaniol, Thomas P.; Maron, Laurent; Okuda, Jun

doi:10.1002/anie.201300749

Cited by 80 publications

(118 citation statements)

References 47 publications

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“…The weak interaction is further demonstrated with the initial adduct A exhibiting elongated metal−C bonding interactions of 2.202 Å (Zn), 2.491 Å (Cd) and 2.821 Å (Hg), which are longer than the sum of covalent radii for metal−C single bonds of 1.93 Å (Zn), 2.11 Å (Cd) and 2.08 Å (Hg) . The Zn–carbene interaction is longer than in the Zn species isolated by Hillmyer and Tolman (2.04 to 2.05 Å, depending on the zinc substituents of chloride or benzyl alcohol), the zinc dihydride bridged NHC i Pr compound synthesized by Maron and Okuda (2.05 Å) as well the Zn–carbene interaction of 2.07 Å reported by Brown and Rivard . The carbene‐stabilized compounds isolated by Roesler and co‐workers yielded metal–carbene distances of 2.00 Å (Zn), 2.25 Å (Cd) and 2.18 Å (Zn).…”

Section: Resultsmentioning

confidence: 92%

Insertion of Group 12–16 Hydrides into NHCs: A Theoretical Investigation

Iversen

Dutton

Wilson

2017

Chemistry An Asian Journal

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Abstract:The endocyclic ring expansiono fN-heterocyclic carbene (NHC) rings by transitionm etal (group 12) and main group (group 13-16) elementh ydrides has been investigated in ac omputational study.I na ddition to previously reported insertion reactivity with Si, B, Be and Zn, similarr eactivity is predicted to be feasible for heavierg roup 13 elements (Al,G a, In, Tl), with the reaction barriersf or Al-Tl calculated to be lower than for boron.I nsertion is not expected with group 15-16 elementh ydrides, as the initial adduct formationist hermodynamically unfavorable. The reaction pathway with group 12 hydrides is calculated to be more favorable with two NHCs rather than as ingle NHC (analogous to Be), however hydride ring insertion with metal dihydrides is not feasible, but ratherareduced NHC is thermodynamically favored. For group 14, ring-insertion reactivityi sp redicted to be feasible with the heavier dihydrides. Trends in reactivity of element hydrides may be related to the protic or hydridic character of the elementhydrides.

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Section: Resultsmentioning

confidence: 92%

Insertion of Group 12–16 Hydrides into NHCs: A Theoretical Investigation

Iversen

Dutton

Wilson

2017

Chemistry An Asian Journal

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“…However, the use of as toichiometric and expensive organometallic additive is as ubstantial drawback for the CO 2 transformation reaction. [47] All of these studies demonstrated the significance of the imidazolate motifs in the NHC building blocks for CO 2 activation and subsequent transformations. [46] They examined various copper/NHC catalysts using their established reaction protocol, and as eries of propiolic acids were efficiently prepared under mild reaction conditions.Areaction mechanism was proposed (Figure 7) in which the copper center activated the terminal alkyne with abase to generate acopper acetylide species and the free NHC activated CO 2 to form the NHC-CO 2 adduct.…”

Section: Methodsmentioning

confidence: 90%

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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“…have described [ZnH 2 (NHC)] 2 (NHC=IDipp, IMes) 9b. Interestingly, reduction of [ZnCp* 2 ] or [ZnH 2 (NHC)] 2 with H 2 at elevated temperatures gave metallic Zn 0 9b. 12 This implies that soluble zinc hydrides can undergo reductive elimination under reducing conditions.…”

Section: Resultsmentioning

confidence: 99%

Zincocene and Dizincocene N‐Heterocyclic Carbene Complexes and Catalytic Hydrogenation of Imines and Ketones

Jochmann

Stephan

2014

Chemistry A European J

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The N-heterocyclic carbene (NHC) adducts Zn(Cp(R))(2) (NHC)] (Cp(R) =C(5)HMe(4), C(5)H(4) SiMe(3); NHC=ItBu, IDipp (Dipp=2,6-diisopropylphenyl), IMes (Mes=mesityl), SIMes) were prepared and shown to be active catalysts for the hydrogenation of imines, whereas decamethylzincocene [ZnCp*(2)] is highly active for the hydrogenation of ketones in the presence of noncoordinating NHCs. The abnormal carbene complex [Zn(OCHPh(2))(2) (aItBu)](2) was formed from spontaneous rearrangement of the ItBu ligand during incomplete hydrogenation of benzophenone. Two isolated Zn(I) adducts [Zn(2)Cp*(2) (NHC)] (NHC=ItBu, SIMes) are presented and characterized as weak adducts on the basis of (13)C NMR spectroscopic and X-ray diffraction experiments. A mechanistic proposal for the reduction of [ZnCp*(2)] with H(2) to give [Zn(2)Cp*(2)] is discussed.

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Molecular Zinc Dihydride Stabilized by N‐Heterocyclic Carbenes

Cited by 80 publications

References 47 publications

Insertion of Group 12–16 Hydrides into NHCs: A Theoretical Investigation

Insertion of Group 12–16 Hydrides into NHCs: A Theoretical Investigation

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

Zincocene and Dizincocene N‐Heterocyclic Carbene Complexes and Catalytic Hydrogenation of Imines and Ketones

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Molecular Zinc Dihydride Stabilized by N‐Heterocyclic Carbenes

Cited by 80 publications

References 47 publications

Insertion of Group 12–16 Hydrides into NHCs: A Theoretical Investigation

Insertion of Group 12–16 Hydrides into NHCs: A Theoretical Investigation

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

Zincocene and Dizincocene N‐Heterocyclic Carbene Complexes and Catalytic Hydrogenation of Imines and Ketones

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