Insights into Formate Oxidation by a Series of Cobalt Piano-Stool Complexes Supported by Bis(phosphino)amine Ligands

被引:8
作者
Cook, Andrew W. [1 ]
Emge, Thomas J. [1 ]
Waldie, Kate M. [1 ]
机构
[1] Rutgers State Univ, Dept Chem & Chem Biol, New Brunswick, NJ 08903 USA
关键词
FORMIC-ACID; STRUCTURAL-CHARACTERIZATION; ETHYLENE TETRAMERIZATION; DIPHOSPHINE CATALYSTS; DEHYDROGENATION; REDUCTION; DESIGN; REACTIVITY; HYDRICITY; MECHANISM;
D O I
10.1021/acs.inorgchem.1c00563
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A series of (cyclopentadienyl)cobalt(III) half-sandwich complexes (1-4) supported by bidentate bis(phosphino)amine ligands was synthesized and characterized by NMR spectroscopy, X-ray crystallography, and cyclic voltammetry. The Co-III- hydride complex 4-H bearing the bis-(cyclohexylphosphine) ligand derivative was successfully isolated via protonation of the neutral reduced Co-I complex 5 with a weak acid. Experimental and computational methods were used to determine the thermodynamic hydride accepting ability of these Co-III centers and to evaluate their reactivity toward the oxidation of formate. We find that the hydride accepting ability of 1-4 ranges from 71 to 74 kcal/mol in acetonitrile, which should favor a highly exergonic reaction with formate through direct hydride transfer. Formate oxidation was demonstrated at elevated temperatures in the presence of stoichiometric quantities of 4, generating carbon dioxide and the Co-III-hydride complex 4-H in 72% yield.
引用
收藏
页码:7372 / 7380
页数:9
相关论文
共 72 条
[1]   Mechanistic studies of the ethylene trimerization reaction with chromium-diphosphine catalysts: Experimental evidence for a mechanism involving metallacyclic intermediates [J].
Agapie, T ;
Schofer, SJ ;
Labinger, JA ;
Bercaw, JE .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (05) :1304-1305
[2]   First-Row Transition Metal (De)Hydrogenation Catalysis Based On Functional Pincer Ligands [J].
Alig, Lukas ;
Fritz, Maximilian ;
Schneider, Sven .
CHEMICAL REVIEWS, 2019, 119 (04) :2681-2751
[3]   Direct formate fuel cells: A review [J].
An, L. ;
Chen, R. .
JOURNAL OF POWER SOURCES, 2016, 320 :127-139
[4]   Where does hydrogen fit in a sustainable energy economy? [J].
Andrews, John ;
Shabani, Bahman .
INTERNATIONAL ENERGY CONGRESS 2012, 2012, 49 :15-25
[5]   Synthesis and characterization of new bis(diphenylphosphino)aniline ligands and their complexes: X-ray crystal structure of palladium(II) and platinum(II) complexes, and application of palladium(II) complexes as pre-catalysts in Heck and Suzuki cross-coupling reactions [J].
Aydemir, Murat ;
Durap, Feyyaz ;
Baysal, Akin ;
Akba, Osman ;
Gumgum, Bahattin ;
Ozkar, Saim ;
Yildirim, Leyla Tatar .
POLYHEDRON, 2009, 28 (12) :2313-2320
[6]   COORDINATION CHEMISTRY OF DIPHOSPHINOAMINE AND CYCLODIPHOSPHAZANE LIGANDS [J].
BALAKRISHNA, MS ;
REDDY, VS ;
KRISHNAMURTHY, SS ;
NIXON, JF ;
STLAURENT, JCTRB .
COORDINATION CHEMISTRY REVIEWS, 1994, 129 (1-2) :1-90
[7]   COMPARISON OF THE SELF-REACTIVITY OF [CPCO(PP)I]+ COMPLEXES, PP = PH2P(CH2)NPPH2 (N = 1-4), LEADING TO BRIDGED AND OXIDIZED DANGLING PP REACTIONS AND SPECTRAL STUDIES AND THE STRUCTURES OF [CPCO(DPPM)I]I.CHCL3, CPCO[DPPM(O)]I2, AND CP2CO2I4(MU-DPPPENT) [J].
BAO, QB ;
LANDON, SJ ;
RHEINGOLD, AL ;
HALLER, TM ;
BRILL, TB .
INORGANIC CHEMISTRY, 1985, 24 (06) :900-908
[8]   Lewis Acid-Assisted Formic Acid Dehydrogenation Using a Pincer-Supported Iron Catalyst [J].
Bielinski, Elizabeth A. ;
Lagaditis, Paraskevi O. ;
Zhang, Yuanyuan ;
Mercado, Brandon Q. ;
Wuertele, Christian ;
Bernskoetter, Wesley H. ;
Hazari, Nilay ;
Schneider, Sven .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (29) :10234-10237
[9]   Ethylene tetramerisation:: Subtle effects exhibited by N-substituted diphosphinoamine ligands [J].
Blann, Kevin ;
Bollmann, Annette ;
de Bod, Henriette ;
Dixon, John T. ;
Killian, Esna ;
Nongodlwana, Palesa ;
Maumela, Munaka C. ;
Maumela, Hulisani ;
McConnell, Ann E. ;
Morgan, David H. ;
Overett, Matthew J. ;
Pretorius, Marie ;
Kuhlmann, Sven ;
Wasserscheid, Peter .
JOURNAL OF CATALYSIS, 2007, 249 (02) :244-249
[10]   Efficient Dehydrogenation of Formic Acid Using an Iron Catalyst [J].
Boddien, Albert ;
Mellmann, Doerthe ;
Gaertner, Felix ;
Jackstell, Ralf ;
Junge, Henrik ;
Dyson, Paul J. ;
Laurenczy, Gabor ;
Ludwig, Ralf ;
Beller, Matthias .
SCIENCE, 2011, 333 (6050) :1733-1736