Metal-directed assembly of metal(II) benzoates (M = Mn, Ni, Co, Cu, Zn, and Cd) with 1,2-bis(4-pyridyl)ethene: Light- and photo-induced [2 + 2] cycloaddition

Kim, Jin Hoon; Bae, Jeong Mi; Lee, Hong Gyu; Kim, Nack Joo; Jung, Kwang‐Deog; Kim, Cheal; Kim, Sung Jin; Kim, Youngmee

doi:10.1016/j.inoche.2012.05.011

Cited by 11 publications

(1 citation statement)

References 40 publications

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“…In the second, photosensitizers harvest light energy and activate cocatalysts to catalyze following reactions, namely dual photocatalysis. In the last one, transition metal complexes play a dual role by absorbing light energy and enabling catalysis, which have been widely developed in the past decade, in particular organometallic Ir, Ru, and Cu complexes. ,,− Their metal-to-ligand charge transfer (MLCT) triplet excited states are long-lived enough to enable a range of applications including C–C cross-coupling, , C–H annelation, and cycloaddition reactions. − …”

Section: Introductionmentioning

confidence: 99%

Roles of Nonadiabatic Processes, Reaction Mechanism, and Selectivity in Cu-Catalyzed [2 + 2] Photocycloaddition of Norbornene and Acetone to Oxetane

Peng,

Jin,

Zhang

et al. 2024

J. Org. Chem.

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Oxetane has been extensively studied for its applications in medicinal chemistry and as a reactive intermediate in synthesis. Experiments report a Cu-catalyzed [2 + 2] photocycloaddition of acetone and norbornene to oxetane, which is proposed to deviate from the conventional Paterno-Buchi reaction. However, its mechanism at the atomic level is not clear. In this study, we used a combination of multistate complete active space second-order perturbation theory (MS-CASPT2) and density functional theory to systematically investigate the reaction mechanism and elucidate the factors contributing to the diastereomeric selectivity. Initially, the formation of the TpCu-(Norb) complex is achieved by strong interaction between tris(pyrazolyl)borate Cu(I) (TpCu) and norbornene in the ground state (S 0 ). Upon photoexcitation, TpCu(Norb) eventually decays to the T 1 state, in which TpCu(Norb) attacks acetone to initiate subsequent reactions and produces final endo-or exo-oxetane products. All these reactions initially involve the C−C bond formation in the T 1 state thereto leading to a ring-opening intermediate. This intermediate then undergoes a nonradiative transition to the S 0 state, producing a five-membered ring intermediate, from which the C−O bond is formed, leading to the experimentally dominant exo-product. In contrast, the endo-oxetane formation requires a rearrangement process after the C−C bond is formed because of the large steric effects. As a consequence, the different reaction pathways generating exo-and endo-products exhibit large differences in the free-energy barriers, which results in a diastereomeric selectivity observed experimentally. Additionally, the nonradiative transition is found to play an important role in facilitating these reaction steps. The present computational study provides valuable mechanistic insights into Cu-catalyzed photocycloaddition reactions.

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Section: Introductionmentioning

confidence: 99%

Roles of Nonadiabatic Processes, Reaction Mechanism, and Selectivity in Cu-Catalyzed [2 + 2] Photocycloaddition of Norbornene and Acetone to Oxetane

Peng,

Jin,

Zhang

et al. 2024

J. Org. Chem.

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Solid‐State Structural Transformations and Photoreactivity of 1D‐Ladder Coordination Polymers of Pb^II

Kole

Peedikakkal

Toh

et al. 2013

Chemistry A European J

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An attempt has been made to design double-stranded ladder-like coordination polymers (CPs) of hemidirected Pb(II) . Four CPs, [Pb(μ-bpe)(O2 C-C6 H5 )2 ]⋅2H2 O (1), [Pb2 (μ-bpe)2 (μ-O2 C-C6 H5 )2 (O2 C-C6 H5 )2 ] (2), [Pb2 (μ-bpe)2 (μ-O2 C-p-Tol)2 (O2 C-p-Tol)2 ]⋅ 1.5 H2 O (3) and [Pb2 (μ-bpe)2 (μ-O2 C-m-Tol)2 (O2 C-m-Tol)2 ] (4) (bpe=1,2-bis(4'-pyridyl)ethylene), have been synthesised and investigated for their solid-state photoreactivity. CPs 2-4, having a parallel orientation of bpe molecules in their ladder structures and being bridged by carboxylates, were found to be photoreactive, whereas CP 1 is a linear one-dimensional (1D) CP with guest water molecules aggregating to form a hydrogen-bonded 1D structure. The linear strands of 1 were found to pair up upon eliminating lattice water molecules by heating, which led to the solid-state structural transformation of photostable linear 1D CP 1 into photoreactive ladder CP 2. In the construction of the double-stranded ladder-like structures, the parallel alignment of CC bonds in 2-4 is dictated by the chelating and μ2 -η(2) :η(1) bridging modes of the benzoate and toluate ligands. The role of solvents in the formation of such double-stranded ladder-like structures has also been investigated. A single-crystal-to-single-crystal transformation occurred when 4 was irradiated under UV light to form [Pb2 (rctt-tpcb)(μ-O2 C-m-Tol)2 (O2 C-m-Tol)2 ] (5).

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Catalytic transesterification reactions of one-dimensional coordination polymers containing paddle-wheel-type units connected by various bridging ligands

Hwang

Kim

et al. 2013

Inorganica Chimica Acta

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Metal-directed assembly of metal(II) benzoates (M = Mn, Ni, Co, Cu, Zn, and Cd) with 1,2-bis(4-pyridyl)ethene: Light- and photo-induced [2 + 2] cycloaddition

Cited by 11 publications

References 40 publications

Roles of Nonadiabatic Processes, Reaction Mechanism, and Selectivity in Cu-Catalyzed [2 + 2] Photocycloaddition of Norbornene and Acetone to Oxetane

Roles of Nonadiabatic Processes, Reaction Mechanism, and Selectivity in Cu-Catalyzed [2 + 2] Photocycloaddition of Norbornene and Acetone to Oxetane

Solid‐State Structural Transformations and Photoreactivity of 1D‐Ladder Coordination Polymers of Pb^II

Catalytic transesterification reactions of one-dimensional coordination polymers containing paddle-wheel-type units connected by various bridging ligands

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Metal-directed assembly of metal(II) benzoates (M = Mn, Ni, Co, Cu, Zn, and Cd) with 1,2-bis(4-pyridyl)ethene: Light- and photo-induced [2 + 2] cycloaddition

Cited by 11 publications

References 40 publications

Roles of Nonadiabatic Processes, Reaction Mechanism, and Selectivity in Cu-Catalyzed [2 + 2] Photocycloaddition of Norbornene and Acetone to Oxetane

Roles of Nonadiabatic Processes, Reaction Mechanism, and Selectivity in Cu-Catalyzed [2 + 2] Photocycloaddition of Norbornene and Acetone to Oxetane

Solid‐State Structural Transformations and Photoreactivity of 1D‐Ladder Coordination Polymers of PbII

Catalytic transesterification reactions of one-dimensional coordination polymers containing paddle-wheel-type units connected by various bridging ligands

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Solid‐State Structural Transformations and Photoreactivity of 1D‐Ladder Coordination Polymers of Pb^II