Solvent Coordination Effect on Copper-Based Molecular Catalysts for Controlled Radical Polymerization
Abstract
:1. Introduction
2. Results and Discussion
2.1. Oxidation of CuI Complexes by the X• Radical
2.2. Solvent Coordination to Copper Complexes
2.2.1. Analysis of Solvent Coordination to Copper(I/II) Centers
2.2.2. CuI/IIL(S)]+/2+ Complexes
2.2.3. Analysis of the Isomers [CuII(PMDETA)X(S)]+
2.3. Reactions including the Explicit Solvent Coordination
3. Materials and Methods
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
References
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Reaction | ΔEr | ΔGr | ||
---|---|---|---|---|
Gas phase | Gas phase | In MeCN 1 | In DMSO 1 | |
[CuI(Me6TREN)]+ + Cl• → [CuII(Me6TREN)Cl]+ | −62.2 | −51.8 | −59.2 | −59.3 |
[CuI(Me6TREN)]+ + Br• → [CuII(Me6TREN)Br]+ | −47.1 | −37.2 | −43.8 | −43.9 |
[CuI(PMDETA)]+ + Cl• → [CuII(PMDETA)Cl]+ | −59.8 | −49.6 | −58.5 | −58.6 |
[CuI(PMDETA)]+ + Br• → [CuII(PMDETA)Br]+ | −44.9 | −35.5 | −43.3 | −43.4 |
[CuI(TPMA)]+ + Cl• → [CuII(TPMA)Cl]+ | −59.1 | −48.9 | −57.1 | −57.1 |
[CuI(TPMA)]+ + Br• → [CuII(TPMA)Br]+ | −44.5 | −34.6 | −42.0 | −42.0 |
Reaction | ΔEr | ΔGr | ||
---|---|---|---|---|
Gas Phase | Gas Phase | In MeCN | In DMSO | |
[CuI(Me6TREN)]+ + AlCl [CuII(Me6TREN)Cl]+ + Al• | 7.3 | 6.1 | 1.0 | 0.9 |
[CuI(Me6TREN)]+ + AlBr [CuII(Me6TREN)Br]+ + Al• | 8.2 | 7.0 | 2.5 | 2.4 |
[CuI(Me6TREN)]+ + EtCliBu [CuII(Me6TREN)Cl]+ + EtiBu• | 10.7 | 7.4 | 1.4 | 1.3 |
[CuI(Me6TREN)]+ + EtBriBu [CuII(Me6TREN)Br]+ + EtiBu• | 11.1 | 7.5 | 2.0 | 2.0 |
[CuI(Me6TREN)]+ + MeClPr [CuII(Me6TREN)Cl]+ + MePr• | 12.1 | 10.3 | 4.4 | 4.3 |
[CuI(Me6TREN)]+ + MeBrPr [CuII(Me6TREN)Br]+ + MePr• | 13.3 | 11.4 | 6.1 | 6.0 |
[CuI(PMDETA)]+ + AlCl [CuII(PMDETA)Cl]+ + Al• | 9.7 | 8.3 | 1.8 | 1.7 |
[CuI(PMDETA)]+ + AlBr [CuII(PMDETA)Br]+ + Al• | 10.4 | 8.7 | 3.0 | 2.9 |
[CuI(PMDETA)]+ + EtCliBu [CuII(PMDETA)Cl]+ + EtiBu• | 13.2 | 9.5 | 2.1 | 2.0 |
[CuI(PMDETA)]+ + EtBriBu [CuII(PMDETA)Br]+ + EtiBu• | 13.3 | 9.2 | 2.6 | 2.5 |
[CuI(PMDETA)]+ + MeClPr [CuII(PMDETA)Cl]+ + MePr• | 14.5 | 12.5 | 5.2 | 5.1 |
[CuI(PMDETA)]+ + MeBrPr [CuII(PMDETA)Br]+ + MePr• | 15.5 | 13.0 | 6.6 | 6.5 |
[CuI(TPMA)]+ + AlCl [CuII(TPMA)Cl]+ + Al• | 10.3 | 9.0 | 3.2 | 3.1 |
[CuI(TPMA)]+ + AlBr [CuII(TPMA)Br]+ + Al• | 10.8 | 9.6 | 4.4 | 4.3 |
[CuI(TPMA)]+ + EtCliBu [CuII(TPMA)Cl]+ + EtiBu• | 13.8 | 10.3 | 3.5 | 3.4 |
[CuI(TPMA)]+ + EtBriBu [CuII(TPMA)Br]+ + EtiBu• | 13.7 | 10.0 | 4.0 | 3.9 |
[CuI(TPMA)]+ + MeClPr [CuII(TPMA)Cl]+ + MePr• | 15.1 | 13.2 | 6.6 | 6.5 |
[CuI(TPMA)]+ + MeBrPr [CuII(TPMA)Br]+ + MePr• | 15.9 | 13.9 | 8.0 | 7.9 |
S | CuI | CuII | ||
---|---|---|---|---|
Gas Phase | In Solvent 1 | Gas Phase | In Solvent 1 | |
MeCN (end-on) | −51.7 | −24.8 | −161.6 | −38.7 |
DMSO-κOα | −57.5 | −23.7 | −208.2 | −86.0 |
DMSO-κOβ | −56.0 | −24.2 | - 2 | - 2 |
DMSO-κS | −35.8 | −15.2 | −183.6 | −71.2 |
Reaction | ΔEr Gas Phase | ΔGr Gas Phase | ΔGr In Solution 1 | ||||||
---|---|---|---|---|---|---|---|---|---|
MeCN | DMSO-κO2 | DMSO-κS | MeCN | DMSO-κO2 | DMSO-κS | MeCN | DMSO-κO2 | DMSO-κS | |
[CuI(Me6TREN)]+ + S [CuI(Me6TREN)(S)]+ | −17.9 | −20.8 | −15.2 | −7.5 | −9.4 | −2.6 | −4.4 | −2.2 | 0.4 |
[CuI(PMDETA]+ + S [CuI(PMDETA)(S)]+ | −23.0 | −24.2 | −19.6 | −12.6 | −11.6 | −5.5 | −6.3 | −3.3 | −2.6 |
[CuI(PMDETA)(S)]+ + S [CuI(PMDETA)(S)2]+ | −11.4 | −18.2 | - | −1.8 | −6.4 | - | 1.7 | 0.2 | - |
[CuI(TPMA)]+ + S [CuI(TPMA)(S)]+ | −16.8 | −18.9 | −13.6 | −6.7 | −7.5 | −1.8 | −4.0 | −2.7 | −0.4 |
[CuII(Me6TREN)]2+ + S [CuII(Me6TREN)(S)]2+ | −44.7 | −55.6 | −30.5 | −33.9 | −41.8 | −16.1 | −10.1 | −32.2 | −11.7 |
[CuII(PMDETA)]2+ + S [CuII(PMDETA)(S)]2+ | −48.7 | −60.3 | - | −36.6 | −46.1 | - | −18.7 | −31.0 | - |
[CuII(PMDETA)(S)]2+ + S [CuII(PMDETA)(S)2]2+ | −29.1 | −38.5 | - | −18.5 | −24.2 | - | −6.3 | −17.0 | - |
[CuII(TPMA)]2+ + S [CuII(TPMA)(S)]2+ | −43.7 | −52.7 | −32.0 | −31.8 | −39.5 | −18.3 | −19.1 | −29.6 | −15.7 |
Isomer | ||||||
---|---|---|---|---|---|---|
ΔEr Gas Phase | ΔGr Gas Phase | ΔGr In MeCN 1 | ΔEr Gas Phase | ΔGr Gas Phase | ΔGr In DMSO 1 | |
I1 | −15.9 | −2.3 | 4.4 | −25.6 | −11.0 | −0.5 |
I2 | −19.4 | −8.1 | −1.1 | −29.7 | −15.1 | −4.7 |
I3 | −11.2 | 0.5 | 4.6 | −25.7 | −11.7 | −3.9 |
I4 | −6.1 | 5.5 | 10.6 | −17.8 | −3.3 | 4.5 |
Reaction | S = MeCN | S = DMSO | ||||
---|---|---|---|---|---|---|
ΔE Gas Phase | ΔGr Gas Phase | ΔGr 1 In Solution | ΔE Gas Phase | ΔGr Gas Phase | ΔGr 1 In Solution | |
[CuI(Me6TREN)(S)]+ + AlCl [CuII(Me6TREN)Cl]+ + Al• + S | 25.2 | 13.6 | 4.7 | 28.1 | 15.4 | 3.8 |
[CuI(Me6TREN)(S)]+ + AlBr [CuII(Me6TREN)Br]+ + Al• + S | 26.1 | 14.5 | 6.2 | 29.0 | 16.4 | 5.4 |
[CuI(Me6TREN)(S)]+ + EtCliBu [CuII(Me6TREN)Cl]+ + EtiBu• + S | 28.6 | 14.9 | 5.1 | 31.5 | 16.7 | 4.2 |
[CuI(Me6TREN)(S)]+ + EtBriBu [CuII(Me6TREN)Br]+ + EtiBu• + S | 29.0 | 15.0 | 5.8 | 31.9 | 16.9 | 4.9 |
[CuI(Me6TREN)(S)]+ + MeClPr [CuII(Me6TREN)Cl]+ + MePr• + S | 30.0 | 17.8 | 8.1 | 32.9 | 19.6 | 7.3 |
[CuI(Me6TREN)(S)]+ + MeBrPr [CuII(Me6TREN)Br]+ + MePr• + S | 31.2 | 18.8 | 9.8 | 34.1 | 20.7 | 9.0 |
[CuI(PMDETA)(S)]+ + AlCl [CuII(PMDETA)Cl]+ + Al• + S | 32.7 | 20.9 | 9.4 | 33.9 | 19.9 | 5.8 |
[CuI(PMDETA)(S)]+ + AlBr [CuII(PMDETA)Br]+ + Al• + S | 33.4 | 21.4 | 10.5 | 34.6 | 20.3 | 7.0 |
[CuI(PMDETA)(S)]+ + EtCliBu [CuII(PMDETA)Cl]+ + EtiBu• + S | 36.1 | 22.2 | 9.7 | 37.3 | 21.2 | 6.2 |
[CuI(PMDETA)(S)]+ + EtBriBu [CuII(PMDETA)Br]+ + EtiBu• + S | 36.3 | 21.8 | 10.1 | 37.5 | 20.8 | 6.6 |
[CuI(PMDETA)(S)]+ + MeClPr [CuII(PMDETA)Cl]+ + MePr• + S | 37.5 | 25.1 | 12.8 | 38.7 | 24.1 | 9.2 |
[CuI(PMDETA)(S)]+ + MeBrPr [CuII(PMDETA)Br]+ + MePr• + S | 38.5 | 25.7 | 14.1 | 39.7 | 24.7 | 10.6 |
[CuI(TPMA)(S)]+ + AlCl [CuII(TPMA)Cl]+ + Al• + S | 27.1 | 15.7 | 7.3 | 29.2 | 16.4 | 5.9 |
[CuI(TPMA)(S)]+ + AlBr [CuII(TPMA)Br]+ + Al• + S | 27.6 | 16.3 | 8.5 | 29.7 | 17.0 | 7.1 |
[CuI(TPMA)(S)]+ + EtCliBu [CuII(TPMA)Cl]+ + EtiBu• + S | 30.6 | 17.0 | 7.6 | 32.6 | 17.7 | 6.2 |
[CuI(TPMA)(S)]+ + EtBriBu [CuII(TPMA)Br]+ + EtiBu• + S | 30.5 | 16.8 | 8.1 | 32.6 | 17.5 | 6.7 |
[CuI(TPMA)(S)]+ + MeClPr [CuII(TPMA)Cl]+ + MePr• + S | 31.9 | 19.9 | 10.7 | 34.0 | 20.6 | 9.3 |
[CuI(TPMA)(S)]+ + MeBrPr [CuII(TPMA)Cl]+ + MePr• + S | 32.7 | 20.6 | 12.1 | 34.8 | 21.3 | 10.7 |
[CuI(PMDETA)(S)]+ + AlCl [CuII(PMDETA)Cl(S)]+ + Al• | 15.0 | 12.4 | 5.8 | 2.7 | 4.6 | −1.0 |
[CuI(PMDETA)(S)]+ + AlBr [CuII(PMDETA)Br(S)]+ + Al• | 14.0 | 14.3 | 9.4 | 4.9 | 5.2 | 2.4 |
[CuI(PMDETA)(S)]+ + EtCliBu [CuII(PMDETA)Cl(S)]+ + EtiBu• | 18.5 | 13.6 | 6.1 | 6.1 | 5.9 | −0.7 |
[CuI(PMDETA)(S)]+ + EtBriBu [CuII(PMDETA)Br(S)]+ + EtiBu• | 16.9 | 13.8 | 9.0 | 7.8 | 5.7 | 2.0 |
[CuI(PMDETA)(S)]+ + MeClPr [CuII(PMDETA)Cl(S)]+ + MePr• | 19.8 | 16.6 | 9.2 | 7.5 | 8.8 | 2.4 |
[CuI(PMDETA)(S)]+ + MeBrPr [CuII(PMDETA)Br(S)]+ + MePr• | 19.1 | 17.6 | 13.0 | 10.0 | 9.6 | 6.0 |
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Racioppi, S.; Orian, L.; Tubaro, C.; Gennaro, A.; Isse, A.A. Solvent Coordination Effect on Copper-Based Molecular Catalysts for Controlled Radical Polymerization. Catalysts 2022, 12, 1656. https://doi.org/10.3390/catal12121656
Racioppi S, Orian L, Tubaro C, Gennaro A, Isse AA. Solvent Coordination Effect on Copper-Based Molecular Catalysts for Controlled Radical Polymerization. Catalysts. 2022; 12(12):1656. https://doi.org/10.3390/catal12121656
Chicago/Turabian StyleRacioppi, Stefano, Laura Orian, Cristina Tubaro, Armando Gennaro, and Abdirisak Ahmed Isse. 2022. "Solvent Coordination Effect on Copper-Based Molecular Catalysts for Controlled Radical Polymerization" Catalysts 12, no. 12: 1656. https://doi.org/10.3390/catal12121656