Unique mononuclear Mn-II complexes of an end-off compartmental Schiff base ligand: experimental and theoretical studies on their bio-relevant catalytic promiscuity

2016
Authors
Adhikary, JaydeepChakraborty, Aratrika
Dasgupta, Sanchari
Chattopadhyay, Shyamal Kumar
Kruszynski, Rafal

Trzesowska-Kruszynska, Agata
Stepanović, Stepan

Gruden-Pavlović, Maja

Swart, Marcel

Das, Debasis
Article (Published version)

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Three new mononuclear manganese(II) complexes, namely [Mn(HL)(2)]center dot 2ClO(4) (1), [Mn(HL)(N(CN)(2)) (H2O)(2)]center dot ClO4 (2) and [Mn(HL)(SCN)(2)] (3) [LH = 4-tert-butyl-2,6-bis-[(2-pyridin-2-yl-ethylimino)-methyl]-phenol], have been synthesized and structurally characterized. An "end-off" compartmental ligand (LH) possesses two symmetrical compartments with N2O binding sites but accommodates only one manganese atom instead of two due to the protonation of the imine nitrogen of one compartment. Although all three complexes are mononuclear, complex 1 is unique as it has a 1 : 2 metal to ligand stoichiometry. The catalytic promiscuity of complexes 1-3 in terms of two different bio-relevant catalytic activities namely catecholase and phenoxazinone synthase has been thoroughly investigated. EPR and cyclic voltametric studies reveal that radical formation rather than metal centered redox participation is responsible for their catecholase-like and phenoxazinone synthase-like cataly...tic activity. A computational approach suggests that imine bond bound radical generation rather than phenoxo radical formation is most likely responsible for the oxidizing properties of the complexes.
Source:
Dalton Transactions, 2016, 45, 31, 12409-12422Publisher:
- Royal Soc Chemistry, Cambridge
Funding / projects:
- ICREA
DOI: 10.1039/c6dt00625f
ISSN: 1477-9226
PubMed: 27430642
WoS: 000381480900019
Scopus: 2-s2.0-84982663415
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IHTMTY - JOUR AU - Adhikary, Jaydeep AU - Chakraborty, Aratrika AU - Dasgupta, Sanchari AU - Chattopadhyay, Shyamal Kumar AU - Kruszynski, Rafal AU - Trzesowska-Kruszynska, Agata AU - Stepanović, Stepan AU - Gruden-Pavlović, Maja AU - Swart, Marcel AU - Das, Debasis PY - 2016 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/1844 AB - Three new mononuclear manganese(II) complexes, namely [Mn(HL)(2)]center dot 2ClO(4) (1), [Mn(HL)(N(CN)(2)) (H2O)(2)]center dot ClO4 (2) and [Mn(HL)(SCN)(2)] (3) [LH = 4-tert-butyl-2,6-bis-[(2-pyridin-2-yl-ethylimino)-methyl]-phenol], have been synthesized and structurally characterized. An "end-off" compartmental ligand (LH) possesses two symmetrical compartments with N2O binding sites but accommodates only one manganese atom instead of two due to the protonation of the imine nitrogen of one compartment. Although all three complexes are mononuclear, complex 1 is unique as it has a 1 : 2 metal to ligand stoichiometry. The catalytic promiscuity of complexes 1-3 in terms of two different bio-relevant catalytic activities namely catecholase and phenoxazinone synthase has been thoroughly investigated. EPR and cyclic voltametric studies reveal that radical formation rather than metal centered redox participation is responsible for their catecholase-like and phenoxazinone synthase-like catalytic activity. A computational approach suggests that imine bond bound radical generation rather than phenoxo radical formation is most likely responsible for the oxidizing properties of the complexes. PB - Royal Soc Chemistry, Cambridge T2 - Dalton Transactions T1 - Unique mononuclear Mn-II complexes of an end-off compartmental Schiff base ligand: experimental and theoretical studies on their bio-relevant catalytic promiscuity VL - 45 IS - 31 SP - 12409 EP - 12422 DO - 10.1039/c6dt00625f ER -
@article{ author = "Adhikary, Jaydeep and Chakraborty, Aratrika and Dasgupta, Sanchari and Chattopadhyay, Shyamal Kumar and Kruszynski, Rafal and Trzesowska-Kruszynska, Agata and Stepanović, Stepan and Gruden-Pavlović, Maja and Swart, Marcel and Das, Debasis", year = "2016", abstract = "Three new mononuclear manganese(II) complexes, namely [Mn(HL)(2)]center dot 2ClO(4) (1), [Mn(HL)(N(CN)(2)) (H2O)(2)]center dot ClO4 (2) and [Mn(HL)(SCN)(2)] (3) [LH = 4-tert-butyl-2,6-bis-[(2-pyridin-2-yl-ethylimino)-methyl]-phenol], have been synthesized and structurally characterized. An "end-off" compartmental ligand (LH) possesses two symmetrical compartments with N2O binding sites but accommodates only one manganese atom instead of two due to the protonation of the imine nitrogen of one compartment. Although all three complexes are mononuclear, complex 1 is unique as it has a 1 : 2 metal to ligand stoichiometry. The catalytic promiscuity of complexes 1-3 in terms of two different bio-relevant catalytic activities namely catecholase and phenoxazinone synthase has been thoroughly investigated. EPR and cyclic voltametric studies reveal that radical formation rather than metal centered redox participation is responsible for their catecholase-like and phenoxazinone synthase-like catalytic activity. A computational approach suggests that imine bond bound radical generation rather than phenoxo radical formation is most likely responsible for the oxidizing properties of the complexes.", publisher = "Royal Soc Chemistry, Cambridge", journal = "Dalton Transactions", title = "Unique mononuclear Mn-II complexes of an end-off compartmental Schiff base ligand: experimental and theoretical studies on their bio-relevant catalytic promiscuity", volume = "45", number = "31", pages = "12409-12422", doi = "10.1039/c6dt00625f" }
Adhikary, J., Chakraborty, A., Dasgupta, S., Chattopadhyay, S. K., Kruszynski, R., Trzesowska-Kruszynska, A., Stepanović, S., Gruden-Pavlović, M., Swart, M.,& Das, D.. (2016). Unique mononuclear Mn-II complexes of an end-off compartmental Schiff base ligand: experimental and theoretical studies on their bio-relevant catalytic promiscuity. in Dalton Transactions Royal Soc Chemistry, Cambridge., 45(31), 12409-12422. https://doi.org/10.1039/c6dt00625f
Adhikary J, Chakraborty A, Dasgupta S, Chattopadhyay SK, Kruszynski R, Trzesowska-Kruszynska A, Stepanović S, Gruden-Pavlović M, Swart M, Das D. Unique mononuclear Mn-II complexes of an end-off compartmental Schiff base ligand: experimental and theoretical studies on their bio-relevant catalytic promiscuity. in Dalton Transactions. 2016;45(31):12409-12422. doi:10.1039/c6dt00625f .
Adhikary, Jaydeep, Chakraborty, Aratrika, Dasgupta, Sanchari, Chattopadhyay, Shyamal Kumar, Kruszynski, Rafal, Trzesowska-Kruszynska, Agata, Stepanović, Stepan, Gruden-Pavlović, Maja, Swart, Marcel, Das, Debasis, "Unique mononuclear Mn-II complexes of an end-off compartmental Schiff base ligand: experimental and theoretical studies on their bio-relevant catalytic promiscuity" in Dalton Transactions, 45, no. 31 (2016):12409-12422, https://doi.org/10.1039/c6dt00625f . .