Influence of induced steric on the switchover reactivity of mononuclear Cu(II)-alkylperoxo complexes

Sayanta Sekhar Nag; Gourab Mukherjee; Prasenjit Barman; Chivukula V. Sastri

doi:10.1016/j.ica.2018.09.087

Influence of induced steric on the switchover reactivity of mononuclear Cu(II)-alkylperoxo complexes

Sayanta Sekhar Nag, Gourab Mukherjee, Prasenjit Barman, Chivukula V. Sastri

School of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract / Description of output

Coordination and steric environment around a metal center plays an indispensable role in its reactivity. In this report we have synthesized two bispidine based Cu(II)-OOR (R = tBu) complexes [Cu(L1)(OOtBu)]+ and [Cu(L2)(OOtBu)]+ having different steric environment around the metal center and characterized by various spectroscopic techniques. These Cu(II)-OOR species show reactivity towards oxygen atom transfer and aldehyde deformylation reactions. In contrast to the previously reported nucleophilic oxidation, aldehyde deformylation reaction by these complexes proceed via an initial H-atom abstraction with KIE of 12 and 8 respectively. It has been observed that more steric bulk at N3 and N7 position of bispidine ligand prefers the oxygen atom transfer reaction while it hinders the H-atom abstraction for Cu(II)-alkylperoxo complexes.

Original language	English
Journal	Inorganica Chimica Acta
Volume	485
Early online date	2 Oct 2018
DOIs	https://doi.org/10.1016/j.ica.2018.09.087
Publication status	E-pub ahead of print - 2 Oct 2018

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title = "Influence of induced steric on the switchover reactivity of mononuclear Cu(II)-alkylperoxo complexes",

abstract = "Coordination and steric environment around a metal center plays an indispensable role in its reactivity. In this report we have synthesized two bispidine based Cu(II)-OOR (R = tBu) complexes [Cu(L1)(OOtBu)]+ and [Cu(L2)(OOtBu)]+ having different steric environment around the metal center and characterized by various spectroscopic techniques. These Cu(II)-OOR species show reactivity towards oxygen atom transfer and aldehyde deformylation reactions. In contrast to the previously reported nucleophilic oxidation, aldehyde deformylation reaction by these complexes proceed via an initial H-atom abstraction with KIE of 12 and 8 respectively. It has been observed that more steric bulk at N3 and N7 position of bispidine ligand prefers the oxygen atom transfer reaction while it hinders the H-atom abstraction for Cu(II)-alkylperoxo complexes.",

author = "Nag, {Sayanta Sekhar} and Gourab Mukherjee and Prasenjit Barman and Sastri, {Chivukula V.}",

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doi = "10.1016/j.ica.2018.09.087",

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T1 - Influence of induced steric on the switchover reactivity of mononuclear Cu(II)-alkylperoxo complexes

AU - Nag, Sayanta Sekhar

AU - Mukherjee, Gourab

AU - Barman, Prasenjit

AU - Sastri, Chivukula V.

PY - 2018/10/2

Y1 - 2018/10/2

N2 - Coordination and steric environment around a metal center plays an indispensable role in its reactivity. In this report we have synthesized two bispidine based Cu(II)-OOR (R = tBu) complexes [Cu(L1)(OOtBu)]+ and [Cu(L2)(OOtBu)]+ having different steric environment around the metal center and characterized by various spectroscopic techniques. These Cu(II)-OOR species show reactivity towards oxygen atom transfer and aldehyde deformylation reactions. In contrast to the previously reported nucleophilic oxidation, aldehyde deformylation reaction by these complexes proceed via an initial H-atom abstraction with KIE of 12 and 8 respectively. It has been observed that more steric bulk at N3 and N7 position of bispidine ligand prefers the oxygen atom transfer reaction while it hinders the H-atom abstraction for Cu(II)-alkylperoxo complexes.

AB - Coordination and steric environment around a metal center plays an indispensable role in its reactivity. In this report we have synthesized two bispidine based Cu(II)-OOR (R = tBu) complexes [Cu(L1)(OOtBu)]+ and [Cu(L2)(OOtBu)]+ having different steric environment around the metal center and characterized by various spectroscopic techniques. These Cu(II)-OOR species show reactivity towards oxygen atom transfer and aldehyde deformylation reactions. In contrast to the previously reported nucleophilic oxidation, aldehyde deformylation reaction by these complexes proceed via an initial H-atom abstraction with KIE of 12 and 8 respectively. It has been observed that more steric bulk at N3 and N7 position of bispidine ligand prefers the oxygen atom transfer reaction while it hinders the H-atom abstraction for Cu(II)-alkylperoxo complexes.

U2 - 10.1016/j.ica.2018.09.087

DO - 10.1016/j.ica.2018.09.087

M3 - Article

SN - 0020-1693

VL - 485

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Influence of induced steric on the switchover reactivity of mononuclear Cu(II)-alkylperoxo complexes

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