A new bis-phenolate mesoionic carbene ligand for early transition metal chemistry

Baltrun, Marc; Watt, Fabian A.; Schoch, Roland; Wölper, Christoph; Neuba, Adam; Hohloch, Stephan

doi:10.1039/c9dt03099a

Cited by 37 publications

(49 citation statements)

References 135 publications

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“…53 iPr OiPr 56a: X = Cl, X' = OiPr 56b: X = X' = Cl 56c: X = X' =OiPr 56d: X = X' = OBn 56e: X = Cl, X' = OSi(OtBu) 3 56f: X = OiPr, X' = OSi(OtBu) 3 56g: Hohloch and co-workers characterized a set of Ti(IV) complexes chelated by a 1,2,3triazolylidene-bis-phenolate tridentate ligand, including hetero-and homo-leptic complexes 68-70 (Figure 9). 56 Such chelates, which are rare examples of abnormal/mesoionic carbene coordination to d 0 -metal center, were shown to be accessible through various routes, including salt metathesis and alcohol elimination reactions. The Ti-oxo species 69 was isolated as a byproduct resulting from partial hydrolysis of 68.…”

Section: Scmentioning

confidence: 99%

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Recent progress on NHC-stabilized early transition metal (group 3–7) complexes: Synthesis and applications

Romain

Bellemin‐Laponnaz

Dagorne

2020

Coordination Chemistry Reviews

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Section: Scmentioning

confidence: 99%

“…82 Hohloch and coworkers investigated the coordination of bis-phenolate mesoionic carbene ligands with group 5 metals (Scheme 34). 56…”

Section: Rh(i)mentioning

confidence: 99%

Recent progress on NHC-stabilized early transition metal (group 3–7) complexes: Synthesis and applications

Romain

Bellemin‐Laponnaz

Dagorne

2020

Coordination Chemistry Reviews

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“… 40 Nevertheless, most studies targeted hitherto late transition metals or main group elements, while early transition-metal complexes with mesoionic carbenes have been rarely explored. 41 − 44 Arguably, this can be attributed to the relatively weak bond between N -heterocyclic carbenes and early transition metals. 45 However, this weak bond may be enhanced by harnessing anionic linkers.…”

Section: Introductionmentioning

confidence: 99%

Mesoionic Carbenes in Low- to High-Valent Vanadium Chemistry

et al. 2021

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We report the synthesis of vanadium(V) oxo complex 1 with a pincer-type dianionic mesoionic carbene (MIC) ligand L 1 and the general formula [VOCl(L 1 )]. A comparison of the structural (SC-XRD), electronic (UV–vis), and electrochemical (cyclic voltammetry) properties of 1 with the benzimidazolinylidene congener 2 (general formula [VOCl(L 2 )]) shows that the MIC is a stronger donor also for early transition metals with low d-electron population. Since electrochemical studies revealed both complexes to be reversibly reduced, the stronger donor character of MICs was not only demonstrated for the vanadium(V) but also for the vanadium(IV) oxidation state by isolating the reduced vanadium(IV) complexes [Co(Cp*) 2 ][1] and [Co(Cp*) 2 ][2] ([Co(Cp*) 2 ] = decamethylcobaltocenium). The electronic structures of the compounds were investigated by computational methods. Complex 1 was found to be a moderate precursor for salt metathesis reactions, showing selective reactivity toward phenolates or secondary amides, but not toward primary amides and phosphides, thiophenols, or aryls/alkyls donors. Deoxygenation with electron-rich phosphines failed to give the desired vanadium(III) complex. However, treatment of the deprotonated ligand precursor with vanadium(III) trichloride resulted in the clean formation of the corresponding MIC vanadium(III) complex 6 , which undergoes a clean two-electron oxidation with organic azides yielding the corresponding imido complexes. The reaction with TMS-N 3 did not afford a nitrido complex, but instead the imido complex 10 . This study reveals that, contrary to popular belief, MICs are capable of supporting early transition-metal complexes in a variety of oxidation states, thus making them promising candidates for the activation of small molecules and redox catalysis.

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“…The structural metrics of the dication in 3 (Table S3) resemble those of previously reported triazolium salts. 98,99 In the solidstate structure of 3, strong hydrogen bonding interactions between the central triazolium nitrogen atoms N3 and the carbazole proton H10 were observed. Due to steric bulk, these interactions are not feasible for the other reported MIC-CNC pincer ligands (Fig.…”

Section: Proligand Synthesismentioning

confidence: 99%

Bright luminescent lithium and magnesium carbene complexes

et al. 2021

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A new bis-phenolate mesoionic carbene ligand for early transition metal chemistry

Abstract: A new chelating mesoionic carbene ligand, derived from 1,2,3-triazoles, with two redox-active tert-butyl-phenolate linkers has been synthesized and explored towards its reactivity and electrochemical properties in early transition metal chemistry.

Cited by 37 publications

References 135 publications

Recent progress on NHC-stabilized early transition metal (group 3–7) complexes: Synthesis and applications

Recent progress on NHC-stabilized early transition metal (group 3–7) complexes: Synthesis and applications

Mesoionic Carbenes in Low- to High-Valent Vanadium Chemistry

Bright luminescent lithium and magnesium carbene complexes

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