Diagonal Relationship among Organometallic Transition-Metal Complexes

Mashima, Kazushi

doi:10.1021/acs.organomet.1c00344

Cited by 17 publications

(22 citation statements)

References 87 publications

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“…Both Schrock carbene catalysts and this family of [V]-carbene above described are high-oxidation early transition metal complexes with similarities, such as bearing ketamide and an alkoxide ligand, as well as the metal center in its highest oxidation center. Because of their position at the periodic table, this can indicate some sort of diagonal relationship …”

Section: Introductionmentioning

confidence: 99%

“…Because of their position at the periodic table, this can indicate some sort of diagonal relationship. 38 The pathway of these [V]-carbene in catalyzing olefin metathesis is remarkable, considering the absence of other successful examples of 3d base metals, especially iron-carbenes attempts, which usually drive to side reactions such as cyclopropanation, primarily because of its multistate nonsinglet reactivity behavior. Hence, in this theoretical work, we aim to understand the reactivity of the [V]-carbene V V ( CHSiMe 3 )(NR)[OC(CF 3 ) 3 ](PMe 3 ) 2 (Scheme 2d) with olefins toward metathesis.…”

Section: ■ Introductionmentioning

confidence: 99%

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Singlet Spin State Drives [V]-Carbene To Catalyze Olefin Metathesis: A Computational Analysis

et al. 2022

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Olefin metathesis is a crucial reaction typically catalyzed by Mo and Ru metal-carbene complexes. Catalysts based on 3d metals have recently attracted much interest due to their abundance, low toxicity, and inexpensive cost. Recently prepared vanadium-carbene complexes with analogous ligands to those of the Schrock carbenes were shown to be effective catalysts for norbornene's ring-opening metathesis polymerization (ROMP). In this work, we employ density functional theory (B3LYP) calculations to explore the reaction mechanism and the energetic performance of the V V (CHSiMe 3 )(NC 6 H 5 )[OC(CF 3 ) 3 ]-(PMe 3 ) 2 (D) complex in catalyzing the ROMP of norbornene. Calculations revealed that the reaction takes place in the singlet spin surface through the classical olefin metathesis mechanism. The electronic analysis indicates the absence of valence electrons in the metallic vanadium d 0 center as a cause in favoring the singlet spin state. The deactivation pathways toward cyclopropanation and βhydride elimination were calculated, and they showed higher barriers than those for olefin metathesis. The replacement of the carbene substituent −SiMe 3 by the substituent −CMe 3 was also analyzed, showing no considerable differences regarding previous catalysts. Our results suggest that the cross-metathesis reaction of styrene catalyzed by the D complex is viable since it presented a potential energy surface similar to that observed in the ROMP reaction of norbornene. The potential energy surfaces of the ROMP reaction catalyzed by D and a Schrock catalyst indicate that the classic molybdenum catalyst favors lower energy barriers compared to vanadium catalysts.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Singlet Spin State Drives [V]-Carbene To Catalyze Olefin Metathesis: A Computational Analysis

et al. 2022

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“…7,8 Among 3d transition metals, OM catalysts based on V have been the most developed, 9 presumably due to the diagonal relationship between V and Mo. 10 V alkylidenes containing imido, alkoxide, and phosphine ligands have been applied the for ring-opening metathesis polymerization (ROMP) of cyclic olefins, showing high activity and selectivity. 11−13 However, those complexes exhibit low productivity toward acyclic terminal olefins.…”

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confidence: 99%

Vanadium Imido NHC Complexes for Ring-Closing Olefin Metathesis Reactions

et al. 2022

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Vanadium bis-phosphine imido and oxo chloride alkylidenes have been extensively applied in the ring-closing metathesis of various acyclic olefins. However, their reactions involving ethylene have shown limited productivity due to rapid decomposition. The primary degradation pathway involving V bis-phosphine imido complexes is β-H elimination at an unsubstituted metallacyclobutane. In contrast, β-H elimination is disfavored for V oxo species, but bimolecular decomposition precludes its high productivity. Herein, we present the synthesis of V imido NHC complexes that are the most productive V catalysts toward various terminal olefins in ring-closing metathesis reactions. Experimental and computational studies suggest that β-H elimination and bimolecular decomposition are disfavored for V imido NHC complexes.

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mentioning

confidence: 88%

“…The diagonal periodic relationships of the early transition metals (i.e., Sc, Zr, and Ta) are well established, which demonstrate that similar reactivity is not only limited within a group but also across groups containing d 0 metals. 12 This identifies early transition metals as ideal candidates to be tested in the pursuit of metal tuning for improvements in crosscoupling. Unfortunately, cross-coupling is not traditionally catalyzed by early transition metals because they typically exist in the d 0 state which means they lack the electrons necessary to undergo oxidative addition and render reductive elimination challenging.…”

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confidence: 99%

Improving Alkyl–Alkyl Cross-Coupling Catalysis with Early Transition Metals through Mechanistic Understanding and Metal Tuning

2022

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Alkyl-alkyl cross-coupling is a powerful C-C bond forming transformation typically catalyzed by late transition metals. Herein we report a mechanistic investigation into an early transition metal-catalyzed variant of this reaction. Through this mechanistic understanding, an ideal Y catalyst was determined through tuning of the metal in order to optimize for oxidation potential, the rate limiting step in this reaction. A wide substrate scope is revealed that includes a variety of functional groups as well as unactivated substrates.

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Diagonal Relationship among Organometallic Transition-Metal Complexes

Cited by 17 publications

References 87 publications

Singlet Spin State Drives [V]-Carbene To Catalyze Olefin Metathesis: A Computational Analysis

Singlet Spin State Drives [V]-Carbene To Catalyze Olefin Metathesis: A Computational Analysis

Vanadium Imido NHC Complexes for Ring-Closing Olefin Metathesis Reactions

Improving Alkyl–Alkyl Cross-Coupling Catalysis with Early Transition Metals through Mechanistic Understanding and Metal Tuning

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