An Azoaromatic Ligand as Four Electron Four Proton Reservoir: Catalytic Dehydrogenation of Alcohols by Its Zinc(II) Complex

被引:52
作者
Pramanick, Rajib [1 ]
Bhattacharje, Rameswar [2 ]
Sengupta, Debabrata [1 ]
Datta, Ayan [2 ]
Goswami, Sreebrata [1 ]
机构
[1] Indian Assoc Cultivat Sci, Dept Inorgan Chem, Kolkata 700032, India
[2] Indian Assoc Cultivat Sci, Dept Spect, Kolkata 700032, India
关键词
HYDROGEN EVOLUTION MECHANISM; DINUCLEAR COPPER COMPLEX; SELECTIVE DEHYDROGENATION; GALACTOSE-OXIDASE; RADICAL COMPLEXES; AEROBIC OXIDATION; MOLECULAR-OXYGEN; TRANSITION-METAL; BOND ACTIVATION; ENERGY-STORAGE;
D O I
10.1021/acs.inorgchem.8b00034
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Electroprotic storage materials, though invaluable in energy-related research, are scanty among non-natural compounds. Herein, we report a zinc(II) complex of the ligand 2,6-bis(phenylazo)pyridine (L), which acts as a multiple electron and proton reservoir during catalytic dehydrogenation of alcohols to aldehydes/ketones. The redox-inactive metal ion Zn(II) serves as an oxophilic Lewis acid, while the ligand behaves as efficient storage of electron and proton. Synthesis, X-ray structure, and spectral characterizations of the catalyst, ZnLCl2 (la) along with the two hydrogenated complexes of la, ZnH2LCl2 (lb), and ZnH4LCl2 (lc) are reported. It has been argued that the reversible azo-hydrazo redox couple of la controls aerobic dehydrogenation of alcohols. Hydrogenated complexes are hyper-reactive and quantitatively reduce O-2 and para-benzoquinone to H2O2 and para-hydroquinone, respectively. Plausible mechanistic pathways for alcohol oxidation are discussed based on controlled experiments, isotope labeling, and spectral analysis of intermediates.
引用
收藏
页码:6816 / 6824
页数:9
相关论文
共 72 条
[1]   A Combined Experimental and Theoretical Investigation on the Role of Halide Ligands on the Catecholase-like Activity of Mononuclear Nickel(II) Complexes with a Phenol-Based Tridentate Ligand [J].
Adhikary, Jaydeep ;
Chakraborty, Prateeti ;
Das, Sudhanshu ;
Chattopadhyay, Tanmay ;
Bauza, Antonio ;
Chattopadhyay, Shyamal Kumar ;
Ghosh, Bipinbihari ;
Mautner, Franz A. ;
Frontera, Antonio ;
Das, Debasis .
INORGANIC CHEMISTRY, 2013, 52 (23) :13442-13452
[2]   A Stable Manganese Pincer Catalyst for the Selective Dehydrogenation of Methanol [J].
Anderez-Fernandez, Maria ;
Vogt, Lydia K. ;
Fischer, Steffen ;
Zhou, Wei ;
Jiao, Haijun ;
Garbe, Marcel ;
Elangovan, Saravanakumar ;
Junge, Kathrin ;
Junge, Henrik ;
Ludwig, Ralf ;
Beller, Matthias .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (02) :559-562
[3]   Reversible catalytic dehydrogenation of alcohols for energy storage [J].
Bonitatibus, Peter J., Jr. ;
Chakraborty, Sumit ;
Doherty, Mark D. ;
Siclovan, Oltea ;
Jones, William D. ;
Soloveichik, Grigorii L. .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2015, 112 (06) :1687-1692
[4]   Towards a general ruthenium-catalyzed hydrogenation of secondary and tertiary amides to amines [J].
Cabrero-Antonino, Jose R. ;
Alberico, Elisabetta ;
Junge, Kathrin ;
Junge, Henrik ;
Beller, Matthias .
CHEMICAL SCIENCE, 2016, 7 (05) :3432-3442
[5]   Outer-Sphere 2e-/2H+ Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes [J].
Cattaneo, Mauricio ;
Ryken, Scott A. ;
Mayer, James M. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (13) :3675-3678
[6]   Manganese Catalyzed α-Olefination of Nitriles by Primary Alcohols [J].
Chakraborty, Subrata ;
Das, Uttam Kumar ;
Ben-David, Yehoshoa ;
Milstein, David .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (34) :11710-11713
[7]   The Formazanate Ligand as an Electron Reservoir: Bis(Formazanate) Zinc Complexes Isolated in Three Redox States [J].
Chang, Mu-Chieh ;
Dann, Thomas ;
Day, David P. ;
Lutz, Martin ;
Wildgoose, Gregory G. ;
Otten, Edwin .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (16) :4118-4122
[8]   ELECTROCHEMICAL PROPERTIES OF [(C5ME5)RHIII(L)CL]+ COMPLEXES (L=2,2'-BIPYRIDINE OR 1,10-PHENANTHROLINE DERIVATIVES) IN SOLUTION AND IN RELATED POLYPYRROLIC FILMS - APPLICATION TO ELECTROCATALYTIC HYDROGEN GENERATION [J].
CHARDONNOBLAT, S ;
COSNIER, S ;
DERONZIER, A ;
VLACHOPOULOS, N .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1993, 352 (1-2) :213-228
[9]   Aerobic oxidation of primary alcohols (including methanol) by copper(II)- and zinc(II)-phenoxyl radical catalysts [J].
Chaudhuri, P ;
Hess, M ;
Müller, J ;
Hildenbrand, K ;
Bill, E ;
Weyhermüller, T ;
Wieghardt, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (41) :9599-9610
[10]   Four-Center Oxidation State Combinations and Near-Infrared Absorption in [Ru(pap)(Q)2]n (Q=3,5-Di-tert-butyl-N-aryl-1,2-benzoquinonemonoimine, pap=2-Phenylazopyridine) [J].
Das, Dipanwita ;
Agarwala, Hemlata ;
Chowdhury, Abhishek Dutta ;
Patra, Tuhin ;
Mobin, Shaikh M. ;
Sarkar, Biprajit ;
Kaim, Wolfgang ;
Lahiri, Goutam Kumar .
CHEMISTRY-A EUROPEAN JOURNAL, 2013, 19 (23) :7384-7394