Photochemistry of copper(II) chlorocomplexes in acetonitrile: Trapping the ligand-to-metal charge transfer excited state relaxations pathways

Mereshchenko, Andrey S.; Olshin, Pavel K.; Karimov, Artur M.; Skripkin, M. Yu.; Burkov, K. A.; Tver’yanovich, Yu. S.; Tarnovsky, Alexander N.

doi:10.1016/j.cplett.2014.10.016

Cited by 51 publications

(60 citation statements)

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“…20,21,32,36,37 The shape and position of the LMCT bands are observed to be similar for acetonitrile and dichloromethane with only a small spectral shift of the absorption maxima. Steady-state absorption spectra of other solutions used in the nanosecond experiments demonstrate that the majority of copper(II) exists in the form of , the predominant form in these solutions, is promoted into the LMCT excited state.…”

Section: Experimental and Computational Methodsmentioning

confidence: 74%

“…Starting from 20 ps, the transient absorption spectra do not change in both the solvents investigated over the full delay time range (1 ns) employed in these experiments, Figure 2. In acetonitrile, these ΔA spectra consisting of the 350−380 and 465 nm ΔA bands (induced absorption) and the negative bleach centered at 405 nm were previously assigned 32,33 to the formation of copper(II) trichloro complexes, the product of ionic dissociation:…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…The lifetime of LMCT excited state is less than 500 fs and the short-time transient absorption spectra (0.5−20 ps) of [CuCl 4 ] 2− are dominated by the absorption of ligand-field excited states. 32,33 The ligand-field excited states have a lifetime less than 5 ps, and therefore, they fully decay at 20 ps after excitation. Starting from 20 ps, the transient absorption spectra do not change in both the solvents investigated over the full delay time range (1 ns) employed in these experiments, Figure 2.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…32 An optical parametric amplifier (OPA) was used to generate 420 nm excitation ("pump") pulses with the energy of 9 μJ pulse −1…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…For this study, we selected copper(II) tetrachloro complexes for several reasons. To begin with, photolysis of [CuCl 4 ] 2− results in ionic dissociation without any reduction of copper(II) ions, 32,33 so that the subsequent recombination of ionic fragment species can be exclusively monitored using transient absorption spectroscopy. Next, this complex has a tractable size for quantum-chemical calculations.…”

Section: Introductionmentioning

confidence: 99%

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Mechanism of Formation of Copper(II) Chloro Complexes Revealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations

et al. 2015

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Copper(II) complexes are extremely labile with typical ligand exchange rate constants on the order of 10 6 −10 9 M −1 s −1 . As a result, it is often difficult to identify the actual formation mechanism of these complexes. In this work, using UV−vis transient absorption when probing in a broad time range (20 ps to 8 μs) in conjunction with DFT/TDDFT calculations, we studied the dynamics and underlying reaction mechanisms of the formation of extremely labile copper(II) CuCl 4 2− chloro complexes from copper(II) CuCl 3 − trichloro complexes and chloride ions. These two species, produced via photochemical dissociation of CuCl 4 2− upon 420 nm excitation into the ligand-to-metal-charge-transfer electronic state, are found to recombine into parent complexes with bimolecular rate constants of (9.0 ± 0.1) × 10 7 and (5.3 ± 0.4) × 10 8 M −1 s −1 in acetonitrile and dichloromethane, respectively. In dichloromethane, recombination occurs via a simple one-step addition. In acetonitrile, where [CuCl 3 ]− reacts with the solvent to form a [CuCl 3 CH 3 CN] − complex in less than 20 ps, recombination takes place via ligand exchange described by the associative interchange mechanism that involves a [CuCl 4 CH 3 CN] 2− intermediate. In both solvents, the recombination reaction is potential energy controlled.

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Section: Experimental and Computational Methodsmentioning

confidence: 74%

Section: Experimental and Computational Methodsmentioning

confidence: 99%

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…32 An optical parametric amplifier (OPA) was used to generate 420 nm excitation ("pump") pulses with the energy of 9 μJ pulse −1…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Mechanism of Formation of Copper(II) Chloro Complexes Revealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations

et al. 2015

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Solvent‐Controlled Copper‐Catalyzed Radical Decarboxylative Coupling for Alkenyl C(sp²)−P Bond Formation

et al. 2017

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The first solvent-controlled copper-catalyzed oxidative decarboxylative coupling of alkenyl acids with P(O)H compoundsf or alkenyl C(sp 2 )ÀPb ond formation by af reeradical process is reported. Ther eactione nables the highly chemo-and stereoselective synthesis of various( E)-alkenylphosphonates and (E)-alkenylphosphinate oxidesi nm oderate to good yields. On the basis of this catalytic system, styr-enes and b-nitrostyrene as well as alkenyl acids can also give the corresponding products by cross-dehydrogenative coupling andd enitration, respectively.B ya lteringt he oxidant, the oxyphosphorylation of styrenes with P(O)H compounds readily yields b-ketophosphonates. The reactiond escribed here enables av ersatile and practical avenue for the formation of valuable CÀPb onds.[a] Dr.Scheme2.Reactionconditions: 1 (0.40 mmol), 2a (0.25 mmol), Cu(OAc) 2 ·H 2 O (7.5 mol %), K 2 S 2 O 8 (0.75 mmol),C H 3 CN (1.0 mL), 24 h, N 2 ;i solatedy ield. Scheme3.Reactionconditions: 1 (0.40 mmol), 2 (0.25 mmol), Cu(OAc) 2 ·H 2 O (7.5 mol %), K 2 S 2 O 8 (0.75 mmol), CH 3 CN (1.0 mL),2 4h,N 2 ;isolated yield. Scheme4.Control experiments. 9 (d, J C-P = 5.3 Hz), 15.4 ppm (d, J C-P = 6.5 Hz); 31 PNMR (162 MHz, CDCl 3 ): d = 19.3 ppm; 19 FNMR (376 MHz, CDCl 3 ): d = À109.8 ppm;H RMS (ESI-TOF): m/z:c alcd for C 12 H 17 FO 3 P: 259.0899 [M+ +H] + ;f ound:2 59.0912;c alcd for C 24 H 33 F 2 O 6 P 2 : 517.1720 [2 M+ +H] + ;found:5 17.1738. Diethyl (E)-(3-fluorostyryl)phosphonate (3 ja). 1 HNMR (400 MHz, CDCl 3 ): d = 7.50-7.24 (m, 4H), 7.20-7.17 (d, 1 HNMR (400 MHz, CDCl 3 ): d = 7.80-7.73 (m, 5H), 7.70-7.68 (d, J = 7.8 Hz, 1H), 7.63-7.47 (m, 9H), 6.98-6.88 ppm (dd, J = 21.8, 17.4 Hz, 1H); 13 CNMR (100 MHz, CDCl 3 ): d = 145.9 (d, J C-P = 3.6 Hz), 135.9 (d, ppm (d, J C-P = 101.9 Hz); 31 PNMR (162 MHz, CDCl 3 ): d = 24.0 ppm; 19 FNMR (376 MHz, CDCl 3 ): d = À62.8 ppm;H RMS (ESI-TOF): m/z: Asian

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Copper Photoredox Catalyzed A3’ Coupling of Arylamines, Terminal Alkynes, and Alcohols through a Hydrogen Atom Transfer Process

2019

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The first successful example of the three-component coupling of N-alkylanilines,terminal alkynes,and alcohols was achieved at room temperature by av isible-light-mediated copper-catalyzed photoredox hydrogen-atom transfer process. This method allows preparation of propargylamines through uniquely selective a-C À Hb ond activation of unactivated alkylalcohols.P reliminary studies indicate that formation of a-oxy radical is operative.T his approach facilitates rapid access to biologically important propargylamines from methanol as an abundant feedstock. Scheme 1. Transition metal catalyzed activation of methanol.

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Photochemistry of copper(II) chlorocomplexes in acetonitrile: Trapping the ligand-to-metal charge transfer excited state relaxations pathways

Cited by 51 publications

References 40 publications

Mechanism of Formation of Copper(II) Chloro Complexes Revealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations

Mechanism of Formation of Copper(II) Chloro Complexes Revealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations

Solvent‐Controlled Copper‐Catalyzed Radical Decarboxylative Coupling for Alkenyl C(sp²)−P Bond Formation

Copper Photoredox Catalyzed A3’ Coupling of Arylamines, Terminal Alkynes, and Alcohols through a Hydrogen Atom Transfer Process

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Photochemistry of copper(II) chlorocomplexes in acetonitrile: Trapping the ligand-to-metal charge transfer excited state relaxations pathways

Cited by 51 publications

References 40 publications

Mechanism of Formation of Copper(II) Chloro Complexes Revealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations

Mechanism of Formation of Copper(II) Chloro Complexes Revealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations

Solvent‐Controlled Copper‐Catalyzed Radical Decarboxylative Coupling for Alkenyl C(sp2)−P Bond Formation

Copper Photoredox Catalyzed A3’ Coupling of Arylamines, Terminal Alkynes, and Alcohols through a Hydrogen Atom Transfer Process

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Solvent‐Controlled Copper‐Catalyzed Radical Decarboxylative Coupling for Alkenyl C(sp²)−P Bond Formation