A Series of [3 + 2] Cycloaddition Products from the Reaction of Rhenium Oxo Complexes with Diphenyl Ketene

Middleditch, Michael; Anderson, James C.; Blake, Alexander J.; Wilson, Claire

doi:10.1021/ic062290b

Cited by 17 publications

(76 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In fact, for propene, all of the relativistic methods yield positive Δ G values, consistent with the experimental observation that simple, unstrained olefins do not react with cationic [Re VII O 3 ] + reagents at room temperature. 37 Interestingly, much smaller variations are observed among the Δ G ⧧ values for the four substrates. Again, for Re, the calculations generally indicate the highest Δ G ⧧ value for propene and lower values for dimethylketene and norbornene.…”

Section: Resultsmentioning

confidence: 93%

Relativity as a Synthesis Design Principle: A Comparative Study of [3 + 2] Cycloaddition of Technetium(VII) and Rhenium(VII) Trioxo Complexes with Olefins

et al. 2021

View full text Add to dashboard Cite

The difference in [3 + 2] cycloaddition reactivity between fac -[MO 3 (tacn)] + (M = Re, 99 Tc; tacn = 1,4,7-triazacyclononane) complexes has been reexamined with a selection of unsaturated substrates including sodium 4-vinylbenzenesulfonate, norbornene, 2-butyne, and 2-methyl-3-butyn-2-ol (2MByOH). None of the substrates was found to react with the Re cation in water at room temperature, whereas the 99 Tc reagent cleanly yielded the [3 + 2] cycloadducts. Interestingly, a bis-adduct was obtained as the sole product for 2MByOH, reflecting the high reactivity of a 99 TcO-enediolato monoadduct. On the basis of scalar relativistic and nonrelativistic density functional theory calculations of the reaction pathways, the dramatic difference in reactivity between the two metals has now been substantially attributed to differences in relativistic effects, which are much larger for the 5d metal. Furthermore, scalar-relativistic Δ G values were found to decrease along the series propene > norbornene > 2-butyne > dimethylketene, indicating major variations in the thermodynamic driving force as a function of the unsaturated substrate. The suggestion is made that scalar-relativistic effects, consisting of greater destabilization of the valence electrons of the 5d elements compared with those of the 4d elements, be viewed as a new design principle for novel 99m Tc/Re radiopharmaceuticals, as well as more generally in heavy-element coordination chemistry.

show abstract

Section: Resultsmentioning

confidence: 93%

Relativity as a Synthesis Design Principle: A Comparative Study of [3 + 2] Cycloaddition of Technetium(VII) and Rhenium(VII) Trioxo Complexes with Olefins

et al. 2021

View full text Add to dashboard Cite

show abstract

“…3,7,19 In the context of anti-cancer therapy, there are currently thirteen β-particleemitting radionuclides used in both clinical practice and in pre-clinical studies. 3 Of these, the 186 Re and 188 Re isotopes have emerged as two of the more promising radioisotopes for use in TRNT. Both 186 Re and 188 Re possess favourable physical characteristics and nuclear properties which offer a myriad of advantages for potential therapeutic applications.…”

Section: Introductionmentioning

confidence: 99%

“…3 Of these, the 186 Re and 188 Re isotopes have emerged as two of the more promising radioisotopes for use in TRNT. Both 186 Re and 188 Re possess favourable physical characteristics and nuclear properties which offer a myriad of advantages for potential therapeutic applications. [20][21][22] These will be discussed later on in this review.…”

Section: Introductionmentioning

confidence: 99%

Bifunctional chelators for radiorhenium: past, present and future outlook

et al. 2022

View full text Add to dashboard Cite

show abstract

“…Experimental and theoretical studies focusing on the mechanism of addition of transition metal-oxo species of the type LReO 3 to the C=C double bonds addition to ketene has been reported (Deubel et al 2001 ; Middleditch et al 2007 ; Herrmann et al 1985 , 1986 , 1994 ).…”

Section: Introductionmentioning

confidence: 99%

“…Middleditch et al ( 2007 ) in an experimental study of the reaction of rhenium (VII) trioxo complexes containing the ligand sets scorpionate, [HB(pz) 3 ]ReO 3 , [Ph-B(pz) 3 ]ReO 3 , and [HC(pz) 3 ]ReO 3 [ReO4] and pyridine/pyridine-type ligands [(4,7-diphenyl-1,10-phen)(Br)-ReO 3 ], [(4,4′-di-tert-butyl-2,2′-dipyridyl)(Cl)ReO 3 ] and [(py) 2 Re(Cl)O 3 ] with diphenyl ketene, isolated six novel [3 + 2] cycloaddition products. The isolated solid products were air-stable and resulted from the formation of a [3 + 2] addition of the O=Re=O motif of the rhenium oxo species across the ketene C=C double bond.…”

Section: Introductionmentioning

confidence: 99%

A computational study of the addition of ReO3L (L = Cl−, CH3, OCH3 and Cp) to ethenone

2016

View full text Add to dashboard Cite

The periselectivity and chemoselectivity of the addition of transition metal oxides of the type ReO3L (L = Cl, CH3, OCH3 and Cp) to ethenone have been explored at the MO6 and B3LYP/LACVP* levels of theory. The activation barriers and reaction energies for the stepwise and concerted addition pathways involving multiple spin states have been computed. In the reaction of ReO3L (L = Cl−, OCH3, CH3 and Cp) with ethenone, the concerted [2 + 2] addition of the metal oxide across the C=C and C=O double bond to form either metalla-2-oxetane-3-one or metalla-2,4-dioxolane is the most kinetically favored over the formation of metalla-2,5-dioxolane-3-one from the direct [3 + 2] addition pathway. The trends in activation and reaction energies for the formation of metalla-2-oxetane-3-one and metalla-2,4-dioxolane are Cp < Cl− < OCH3 < CH3 and Cp < OCH3 < CH3 < Cl− and for the reaction energies are Cp < OCH3 < Cl− < CH3 and Cp < CH3 < OCH3 < Cl CH3. The concerted [3 + 2] addition of the metal oxide across the C=C double of the ethenone to form species metalla-2,5-dioxolane-3-one is thermodynamically the most favored for the ligand L = Cp. The direct [2 + 2] addition pathways leading to the formations of metalla-2-oxetane-3-one and metalla-2,4-dioxolane is thermodynamically the most favored for the ligands L = OCH3 and Cl−. The difference between the calculated [2 + 2] activation barriers for the addition of the metal oxide LReO3 across the C=C and C=O functionalities of ethenone are small except for the case of L = Cl− and OCH3. The rearrangement of the metalla-2-oxetane-3-one–metalla-2,5-dioxolane-3-one even though feasible, are unfavorable due to high activation energies of their rate-determining steps. For the rearrangement of the metalla-2-oxetane-3-one to metalla-2,5-dioxolane-3-one, the trends in activation barriers is found to follow the order OCH3 < Cl− < CH3 < Cp. The trends in the activation energies for the most favorable [2 + 2] addition pathways for the LReO3–ethenone system is CH3 > CH3O− > Cl− > Cp. For the analogous ethylene–LReO3 system, the trends in activation and reaction energies for the most favorable [3 + 2] addition pathway is CH3 > CH3O− > Cl− > Cp [10]. Even though the most favored pathway in the ethylene-LReO3 system is the [3 + 2] addition pathway and that on the LReO3–ethenone is the [2 + 2] addition pathway, the trends in the activation energies for both pathways are the same, i.e. CH3 > CH3O− > Cl− > Cp. However, the trends in reaction energies are quite different due to different product stabilities. The formation of the acetic acid precursor through the direct addition pathways was unsuccessful for all the ligands studied. The formation of the acetic acid precursor through the cyclization of the metalla-2-oxetane-3-one is only possible for the ligands L = Cl−, CH3 whiles for the cyclization of metalla-2-oxetane-4-one to the acetic acid precursor is only possible for the ligand L = CH3. Although there are spin-crossover reaction observed for the ligands L = Cl−, CH3 and CH3O−, the reactions occur...

show abstract

A Series of [3 + 2] Cycloaddition Products from the Reaction of Rhenium Oxo Complexes with Diphenyl Ketene

Cited by 17 publications

References 47 publications

Relativity as a Synthesis Design Principle: A Comparative Study of [3 + 2] Cycloaddition of Technetium(VII) and Rhenium(VII) Trioxo Complexes with Olefins

Relativity as a Synthesis Design Principle: A Comparative Study of [3 + 2] Cycloaddition of Technetium(VII) and Rhenium(VII) Trioxo Complexes with Olefins

Bifunctional chelators for radiorhenium: past, present and future outlook

A computational study of the addition of ReO3L (L = Cl−, CH3, OCH3 and Cp) to ethenone

Contact Info

Product

Resources

About