Dehydrogenation of hydrocarbons with metal-carbon multiple bonds and trapping of a titanium(II) intermediate.
作者： Anne K. Hickey , Marco G. Crestani , Alison R. Fout , Xinfeng Gao , Chun-Hsing Chen
DOI: 10.1039/C4DT01037J
关键词: Photochemistry 、 Crystallography 、 Titanium 、 Cyclohexene 、 Metal 、 Ligand 、 Chemistry 、 Moiety 、 Unpaired electron 、 Cyclohexane 、 Dehydrogenation
摘要: Reacting (PNP)TiCHtBu(CH2tBu) with 2,2′-bipyridine (bipy) in cyclohexane or heptane results dehydrogenation, cleanly producing cyclohexene and 1-heptene, respectively, a TiII intermediate that is trapped by bipy to produce [(PNP)TiIII(CH2tBu)(bipy˙−)] (1). This titanium(II) reduces the ligand upon coordination form TiIII center, where unpaired electron antiferromagnetically coupled of reduced [bipy˙−] π-radical moiety, giving an overall diamagnetic species. Complex 1 has been characterized NMR UV-vis spectroscopies as well single crystal X-ray diffraction studies.
rsc.org
sci-hub.se 参考文章(21)
R. John Errington, Advanced Practical Inorganic and Metalorganic Chemistry ,(1997)
Madeleine Schultz, James M. Boncella, David J. Berg, T. Don Tilley, Richard A. Andersen, Coordination of 2,2‘-Bipyridyl and 1,10-Phenanthroline to Substituted Ytterbocenes: An Experimental Investigation of Spin Coupling in Lanthanide Complexes Organometallics. ,vol. 21, pp. 460- 472 ,(2002) , 10.1021/OM010661K
Kotohiro Nomura, Yasukazu Saito, n-Alkene and dihydrogen formation from n-alkanes by photocatalysis using carbonyl(chloro)phosphine–rhodium complexes Journal of The Chemical Society, Chemical Communications. pp. 161- 162 ,(1988) , 10.1039/C39880000161
Marco G. Crestani, Anne K. Hickey, Xinfeng Gao, Balazs Pinter, Vincent N. Cavaliere, Jun-Ichi Ito, Chun-Hsing Chen, Daniel J. Mindiola, Room Temperature Dehydrogenation of Ethane, Propane, Linear Alkanes C4–C8, and Some Cyclic Alkanes by Titanium–Carbon Multiple Bonds Journal of the American Chemical Society. ,vol. 135, pp. 14754- 14767 ,(2013) , 10.1021/JA4060178
Mark Irwin, Rhiannon K. Jenkins, Mark S. Denning, Tobias Krämer, Fernande Grandjean, Gary J. Long, Radovan Herchel, John E. McGrady, Jose M. Goicoechea, Experimental and computational study of the structural and electronic properties of Fe(II)(2,2'-bipyridine)(mes)2 and [Fe(II)(2,2'-bipyridine)(mes)2]-, a complex containing a 2,2'-bipyridyl radical anion. Inorganic Chemistry. ,vol. 49, pp. 6160- 6171 ,(2010) , 10.1021/IC100817S
Alison R. Fout, Brad C. Bailey, Dominik M. Buck, Hongjun Fan, John C. Huffman, Mu-Hyun Baik, Daniel J. Mindiola, Synthetic and Mechanistic Studies of the Ring Opening and Denitrogenation of Pyridine and Picolines by Ti−C Multiple Bonds† Organometallics. ,vol. 29, pp. 5409- 5422 ,(2010) , 10.1021/OM100404D
Oleg V. Ozerov, Carolyn P. Brock, Shana D. Carr, Folami T. Ladipo, Unusual Reductive Coupling of Alkynes and Ketones: Reactivity of Titanacycles Supported by Dimethylsilylcalix[4]arene (DMSC) Ligands Organometallics. ,vol. 19, pp. 5016- 5025 ,(2000) , 10.1021/OM0005349
Loren D. Durfee, Phillip E. Fanwick, Ian P. Rothwell, Kirsten Folting, John C. Huffman, Reductive elimination pathways to low valent titanium aryl oxide complexes Journal of the American Chemical Society. ,vol. 109, pp. 4720- 4722 ,(1987) , 10.1021/JA00249A045
David Owiny, Jesudoss V. Kingston, Marc Maynor, Sean Parkin, Jeff W. Kampf, Folami T. Ladipo, Reductive coupling of [(RO)2Ti(L2)2] complexes containing a chelating bis(aryloxide) ligand with ketones (L2 = bpy, dmbpy, or phen) Organometallics. ,vol. 24, pp. 3995- 4002 ,(2005) , 10.1021/OM050231K
Brad C. Bailey, Hongjun Fan, Erich W. Baum, John C. Huffman, Mu-Hyun Baik, Daniel J. Mindiola, Intermolecular C−H Bond Activation Promoted by a Titanium Alkylidyne Journal of the American Chemical Society. ,vol. 127, pp. 16016- 16017 ,(2005) , 10.1021/JA0556934