Bioinspired oxidation of benzyl alcohol: The role of environment and nuclearity of the catalyst evaluated by multivariate analysis

Chimilouski, Larissa; Morgan, Fredricka; Ekanayake, Danushka; El-Harakeh, Nour; Peralta, Rosely A.; Martendal, Edmar; Verani, Cláudio N.; Xavier, Fernando R.

doi:10.1016/j.jinorgbio.2022.112095

Bioinspired oxidation of benzyl alcohol: The role of environment and nuclearity of the catalyst evaluated by multivariate analysis

Journal Article · Mon Dec 12 00:00:00 EST 2022 · Journal of Inorganic Biochemistry

DOI:https://doi.org/10.1016/j.jinorgbio.2022.112095· OSTI ID:2417748

Chimilouski, Larissa ^[1]; Morgan, Fredricka ^[2]; Ekanayake, Danushka ^[2]; El-Harakeh, Nour ^[2]; Peralta, Rosely A. ^[3]; Martendal, Edmar ^[4]; Verani, Cláudio N. ^[2]; Xavier, Fernando R. ^[4]

Universidade do Estado de Santa Catarina, Joinville (Brazil); OSTI
Wayne State Univ., Detroit, MI (United States)
Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil)
Universidade do Estado de Santa Catarina, Joinville (Brazil)

Inspired by copper-containing enzymes such as galactose oxidase and catechol oxidase, in which distinct coordination environments and nuclearities lead to specific catalytic activities, we summarize here the catalytic properties of dinuclear and mononuclear copper species towards benzyl alcohol oxidation using a multivariate statistical approach. Here, the new dinuclear [Cu₂(μ-L¹)(μ-pz)]²⁺ (1) is compared against the mononuclear [CuL²Cl] (2), where (L¹)^- and (L²)^- are the respective deprotonated forms of 2,6-bis((bis(pyridin-2-ylmethyl)amino)methyl)-4-methylphenol, and 3-((bis(pyridin-2-ylmethyl)amino)methyl)-2-hydroxy-5-methylbenzaldehyde and (pz)^- is a pyrazolato bridge. Copper(II) perchlorate (CP) is used as control. The catalytic oxidation of benzyl alcohol is pursued, aiming to assess the role of the ligand environment and nuclearity. The multivariate statistical approach allows for the search of optimal catalytic conditions, considering variables such as catalyst load, hydrogen peroxide load, and time. Species 1, 2 and CP promoted selective production of benzaldehyde at different yields, with only negligible amounts of benzoic acid. Under normalized conditions, 2 showed superior catalytic activity. This species is 3.5-fold more active than the monometallic control CP, and points out to the need for an efficient ligand framework. Species 2 is 6-fold more active than the dinuclear 1, and indicates the favored nuclearity for the conversion of alcohols into aldehydes.

View Accepted Manuscript (DOE)

Research Organization:: Wayne State Univ., Detroit, MI (United States)

Sponsoring Organization:: National Council for Scientific and Technological Development (CNPq); São Paulo Research Foundation (FAPESP); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001907

OSTI ID:: 2417748

Alternate ID(s):: OSTI ID: 1960901

Journal Information:: Journal of Inorganic Biochemistry, Journal Name: Journal of Inorganic Biochemistry Journal Issue: C Vol. 240; ISSN 0162-0134

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (42)

Aerobic Oxidation of Primary Alcohols by a New Mononuclear CuII-Radical Catalyst Chaudhuri, Phalguni; Hess, Martina; Weyhermüller, Thomas Angewandte Chemie International Edition, Vol. 38, Issue 8 https://doi.org/10.1002/(SICI)1521-3773(19990419)38:8<1095::AID-ANIE1095>3.0.CO;2-I	journal	April 1999
Metal-Free and Copper-Promoted Single-Pot Hydrocarboxylation of Cycloalkanes to Carboxylic Acids in Aqueous Medium Kirillova, MarinaâV.; Kirillov, AlexanderâM.; Pombeiro, Armando J. âL. Advanced Synthesis & Catalysis, Vol. 351, Issue 17 https://doi.org/10.1002/adsc.200900537	journal	November 2009
Benzyl Alcohol Oxidation on Carbon-Supported Pd Nanoparticles: Elucidating the Reaction Mechanism Savara, Aditya; Chan-Thaw, Carine E.; Rossetti, Ilenia ChemCatChem, Vol. 6, Issue 12 https://doi.org/10.1002/cctc.201402552	journal	September 2014
Amavadin and Other Vanadium Complexes as Remarkably Efficient Catalysts for One-Pot Conversion of Ethane to Propionic and Acetic Acids Kirillova, Marina V.; Kuznetsov, Maxim L.; da Silva, José A. L. Chemistry - A European Journal, Vol. 14, Issue 6 https://doi.org/10.1002/chem.200700980	journal	February 2008
Molecular Recognition and Scavenging of Arsenate from Aqueous Solution Using Dimetallic Receptors Moffat, Chris D.; Weiss, Dominik J.; Shivalingam, Arun Chemistry - A European Journal, Vol. 20, Issue 51 https://doi.org/10.1002/chem.201404723	journal	October 2014
Synthesis and Characterization of Copper Complexes of a Tetrapyridyl Ligand, and Their Use in the Catalytic Aerobic Oxidation of Benzyl Alcohol Gamba, Ilaria; Mutikainen, Ilpo; Bouwman, Elisabeth European Journal of Inorganic Chemistry, Vol. 2013, Issue 1 https://doi.org/10.1002/ejic.201200807	journal	November 2012
Tyrosinase: a comprehensive review of its mechanism Sánchez-Ferrer, Álvaro; Neptuno Rodríguez-López, José; García-Cánovas, Francisco Biochimica et Biophysica Acta (BBA) - Protein Structure and Molecular Enzymology, Vol. 1247, Issue 1 https://doi.org/10.1016/0167-4838(94)00204-T	journal	February 1995
Catechol oxidase — structure and activity Eicken, Christoph; Krebs, Bernt; Sacchettini, James C. Current Opinion in Structural Biology, Vol. 9, Issue 6 https://doi.org/10.1016/S0959-440X(99)00029-9	journal	December 1999
The radical chemistry of galactose oxidase Whittaker, James W. Archives of Biochemistry and Biophysics, Vol. 433, Issue 1 https://doi.org/10.1016/j.abb.2004.08.034	journal	January 2005
Aerobic oxidation of benzylic alcohols with bis(3,5-di-tert-butylsalicylaldimine)copper(II) complexes Ahmad, Jahir Uddin; Figiel, Pawel J.; Räisänen, Minna T. Applied Catalysis A: General, Vol. 371, Issue 1-2 https://doi.org/10.1016/j.apcata.2009.09.011	journal	December 2009
Multicopper complexes and coordination polymers for mild oxidative functionalization of alkanes Kirillov, Alexander M.; Kirillova, Marina V.; Pombeiro, Armando J. L. Coordination Chemistry Reviews, Vol. 256, Issue 23-24 https://doi.org/10.1016/j.ccr.2012.07.022	journal	December 2012
Mannich base Cu(II) complexes as biomimetic oxidative catalyst Kundu, Bidyut Kumar; Ranjan, Rishi; Mukherjee, Attreyee Journal of Inorganic Biochemistry, Vol. 195 https://doi.org/10.1016/j.jinorgbio.2019.03.023	journal	June 2019
Oxidation of benzyl alcohols to benzaldehydes in water catalyzed by a Cu(II) complex with a zwitterionic calix[4]arene ligand Gao, Jun; Ren, Zhi-Gang; Lang, Jian-Ping Journal of Organometallic Chemistry, Vol. 792 https://doi.org/10.1016/j.jorganchem.2015.02.008	journal	September 2015
Synthesis, characterization, electrochemical studies and catecholase-like activity of a series of mononuclear Cu(II), homodinuclear Cu(II)Cu(II) and heterodinuclear Cu(II)Ni(II) complexes of a phenol-based compartmental ligand Boghaei, Davar M.; Behzad, Mahdi; Bezaatpour, Abolfazl Journal of Molecular Catalysis A: Chemical, Vol. 241, Issue 1-2 https://doi.org/10.1016/j.molcata.2005.06.064	journal	November 2005
Mild aerobic oxidation of benzyl alcohols to benzaldehydes in water catalyzed by aqua-soluble multicopper(II) triethanolaminate compounds Figiel, Paweł J.; Kirillov, Alexander M.; Karabach, Yauhen Yu. Journal of Molecular Catalysis A: Chemical, Vol. 305, Issue 1-2 https://doi.org/10.1016/j.molcata.2009.01.002	journal	June 2009
New copper(II) dimer with 3-(2-hydroxy-4-nitrophenylhydrazo)pentane-2,4-dione and its catalytic activity in cyclohexane and benzyl alcohol oxidations Mahmudov, Kamran T.; Kopylovich, Maximilian N.; Silva, M. Fátima C. Guedes da Journal of Molecular Catalysis A: Chemical, Vol. 318, Issue 1-2 https://doi.org/10.1016/j.molcata.2009.11.006	journal	March 2010
Biocatalytic oxidation of benzyl alcohol to benzaldehyde via hydrogen transfer Orbegozo, Thomas; Lavandera, Iván; Fabian, Walter M. F. Tetrahedron, Vol. 65, Issue 34 https://doi.org/10.1016/j.tet.2009.06.088	journal	August 2009
Redox Noninnocence of the Bridge in Copper(II) Salophen and Bis(oxamato) Complexes de Bellefeuille, David; Orio, Maylis; Barra, Anne-Laure Inorganic Chemistry, Vol. 54, Issue 18 https://doi.org/10.1021/acs.inorgchem.5b01285	journal	September 2015
Bimetallic Complexes Supported by a Redox-Active Ligand with Fused Pincer-Type Coordination Sites Wang, Denan; Lindeman, Sergey V.; Fiedler, Adam T. Inorganic Chemistry, Vol. 54, Issue 17 https://doi.org/10.1021/acs.inorgchem.5b01380	journal	August 2015
Copper Active Sites in Biology Solomon, Edward I.; Heppner, David E.; Johnston, Esther M. Chemical Reviews, Vol. 114, Issue 7 https://doi.org/10.1021/cr400327t	journal	January 2014
Mechanisms Whereby Mononuclear Copper Proteins Functionalize Organic Substrates Klinman, Judith P. Chemical Reviews, Vol. 96, Issue 7 https://doi.org/10.1021/cr950047g	journal	January 1996
Copper/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Mechanistic Assessment of Different Catalyst Systems Hoover, Jessica M.; Ryland, Bradford L.; Stahl, Shannon S. ACS Catalysis, Vol. 3, Issue 11 https://doi.org/10.1021/cs400689a	journal	October 2013
Dicopper(II) Complexes of H-BPMP-Type Ligands: pH-Induced Changes of Redox, Spectroscopic ( ¹⁹ F NMR Studies of Fluorinated Complexes), Structural Properties, and Catecholase Activities Belle, C.; Beguin, C.; Gautier-Luneau, I. Inorganic Chemistry, Vol. 41, Issue 3 https://doi.org/10.1021/ic010534g	journal	February 2002
Ferrocene as an internal standard for electrochemical measurements Gagne, Robert R.; Koval, Carl A.; Lisensky, George C. Inorganic Chemistry, Vol. 19, Issue 9 https://doi.org/10.1021/ic50211a080	journal	September 1980
pH-Controlled Change of the Metal Coordination in a Dicopper(II) Complex of the Ligand H−BPMP: Crystal Structures, Magnetic Properties, and Catecholase Activity Torelli, S.; Belle, C.; Gautier-Luneau, I. Inorganic Chemistry, Vol. 39, Issue 16 https://doi.org/10.1021/ic991450z	journal	August 2000
Models for iron-oxo proteins. Structures and properties of FeIIFeIII, ZnIIFeIII, and FeIIGaIII complexes with (.mu.-phenoxo)bis(.mu.-carboxylato)dimetal cores Borovik, A. S.; Papaefthymiou, Vasilios; Taylor, Lucille F. Journal of the American Chemical Society, Vol. 111, Issue 16 https://doi.org/10.1021/ja00198a032	journal	August 1989
Radical-Initiated Functionalization of Methane and Ethane in Fuming Sulfuric Acid Basickes, Naomi; Hogan, Terrence E.; Sen, Ayusman Journal of the American Chemical Society, Vol. 118, Issue 51 https://doi.org/10.1021/ja9632365	journal	January 1996
Catalytic Mechanism of Galactose Oxidase: A Theoretical Study Himo, Fahmi; Eriksson, Leif A.; Maseras, Feliu Journal of the American Chemical Society, Vol. 122, Issue 33 https://doi.org/10.1021/ja994527r	journal	August 2000
Copper Centers in the Cryo-EM Structure of Particulate Methane Monooxygenase Reveal the Catalytic Machinery of Methane Oxidation Chang, W. -H.; Lin, H. -H.; Tsai, I-K. Journal of the American Chemical Society, Vol. 143, Issue 26 https://doi.org/10.1021/jacs.1c04082	journal	June 2021
Deciphering the oxygen activation mechanism at the CuC site of particulate methane monooxygenase Peng, Wei; Qu, Xiaoyang; Shaik, Sason Nature Catalysis, Vol. 4, Issue 4 https://doi.org/10.1038/s41929-021-00591-4	journal	April 2021
Magnetic and structural properties of dinuclear singly bridged-phenoxido metal( ii ) complexes Massoud, Salah S.; Spell, Mark; Ledet, Catherine C. Dalton Transactions, Vol. 44, Issue 5 https://doi.org/10.1039/C4DT03508A	journal	January 2015
Synthesis, structure and magnetic characterization of dinuclear copper( ii ) complexes bridged by bicompartmental phenolate Massoud, Salah S.; Junk, Thomas; Louka, Febee R. RSC Advances, Vol. 5, Issue 106 https://doi.org/10.1039/C5RA19358C	journal	January 2015
Multivariate analysis applied to oxidation of cyclohexane and benzyl alcohol promoted by mononuclear iron and copper complexes Vailati, Andrei F.; Huelsmann, Ricardo D.; Martendal, Edmar New Journal of Chemistry, Vol. 44, Issue 6 https://doi.org/10.1039/C9NJ05534G	journal	January 2020
Hydrogen-atom and oxygen-atom transfer reactivities of iron(iv)-oxo complexes of quinoline-substituted pentadentate ligands Munshi, Sandip; Sinha, Arup; Yiga, Solomon Dalton Transactions, Vol. 51, Issue 3 https://doi.org/10.1039/D1DT03381F	journal	January 2022
Synthesis, structure, and spectroscopic properties of copper( II ) compounds containing nitrogen–sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper( II ) perchlorate Addison, Anthony W.; Rao, T. Nageswara; Reedijk, Jan J. Chem. Soc., Dalton Trans., Issue 7 https://doi.org/10.1039/DT9840001349	journal	January 1984
Alkanes to carboxylic acids in aqueous medium: metal-free and metal-promoted highly efficient and mild conversions Kirillova, Marina V.; Kirillov, Alexander M.; Kuznetsov, Maxim L. Chemical Communications, Issue 17 https://doi.org/10.1039/b900853e	journal	January 2009
l-Proline: an efficient N,O-bidentate ligand for copper-catalyzed aerobic oxidation of primary and secondary benzylic alcohols at room temperature Zhang, Guofu; Han, Xingwang; Luan, Yuxin Chemical Communications, Vol. 49, Issue 72 https://doi.org/10.1039/c3cc44122a	journal	January 2013
Insights into metalloenzyme microenvironments: biomimetic metal complexes with a functional second coordination sphere Zhao, Meng; Wang, Hai-Bo; Ji, Liang-Nian Chemical Society Reviews, Vol. 42, Issue 21 https://doi.org/10.1039/c3cs60162e	journal	January 2013
Some New Three Level Designs for the Study of Quantitative Variables Box, G. E. P.; Behnken, D. W. Technometrics, Vol. 2, Issue 4 https://doi.org/10.1080/00401706.1960.10489912	journal	November 1960
Benzoic acid and its derivatives as naturally occurring compounds in foods and as additives: Uses, exposure, and controversy del Olmo, Ana; Calzada, Javier; Nuñez, Manuel Critical Reviews in Food Science and Nutrition, Vol. 57, Issue 14 https://doi.org/10.1080/10408398.2015.1087964	journal	November 2015
Particulate methane monooxygenase contains only mononuclear copper centers Ross, Matthew O.; MacMillan, Fraser; Wang, Jingzhou Science, Vol. 364, Issue 6440 https://doi.org/10.1126/science.aav2572	journal	May 2019
Synthesis and Properties of Binuclear Cobalt(Ii) Oxygen Adduct with 2,6-Bis[Bis(2-Pyridylmethyl)Aminomethyl]-4-Methylphenol Suzuki, Masatatsu; Kanatomi, Hajime; Murase, Ichiro Chemistry Letters, Vol. 10, Issue 12 https://doi.org/10.1246/cl.1981.1745	journal	December 1981

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Benzyl alcohol oxidation
Biochemistry & Molecular Biology
Bioinspired copper complexes
Chemistry
Copper enzymes
Ligand framework
Multivariate analysis
Nuclearity

Bioinspired oxidation of benzyl alcohol: The role of environment and nuclearity of the catalyst evaluated by multivariate analysis

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