Unexpected selectivities in C-H activations of toluene and p-xylene at cationic platinum(II) diimine complexes. New mechanistic insight into product-determining factors.
作者： Lars Johansson , Olav B. Ryan , Christian Rømming , Mats Tilset
DOI: 10.1021/JA010277E
关键词:
摘要: The CH activation of toluene and p-xylene at cationic PtII diimine complexes (NN)Pt(CH3)(H2O)+BF4- (NN = ArNCMeCMeNAr; 1(BF4-), NfNf, Ar 3,5-(CF3)2C6H3); 2(BF4-), N‘N‘, 2,6-(CH3)2C6H3) has been investigated. reactions were performed ambient temperature in 2,2,2-trifluoroethanol (TFE), after complete conversion the starting material to mixtures Pt-aryl/Pt-benzyl methane, acetonitrile was added trap products as more stable adducts. In with toluene, relative amounts resulting from aromatic found decrease order (NN)Pt(m-tolyl)(NCMe)+ > (NN)Pt(p-tolyl)(NCMe)+ (NN)Pt(o-tolyl)(NCMe)+ for both 1 2. Unlike reaction 1, significant benzylic product (N‘N‘)Pt(benzyl)(NCMe)+ concurrently formed revealed an even remarkable difference between Here, ratios (NN)Pt(xylyl...
acs.org
sci-hub.se 参考文章(47)
Peter Burger, Robert G. Bergman, Facile intermolecular activation of carbon-hydrogen bonds in methane and other hydrocarbons and silicon-hydrogen bonds in silanes with the iridium(III) complex Cp*(PMe3)Ir(CH3)(OTf) Journal of the American Chemical Society. ,vol. 115, pp. 10462- 10463 ,(1993) , 10.1021/JA00075A113
G.B. Shul'pin, G.V. Nizova, A.T. Nikitaev, The reaction of PtCl62− with aromatic compounds to afford anionic σ-aryl complexes of platinum(IV): VIII. Kinetics and mechanisms of thermal, photochemical and γ-induced reactions with arenes and arylmercury compounds (electrophilic substitution involving electron transfer)☆ Journal of Organometallic Chemistry. ,vol. 276, pp. 115- 153 ,(1984) , 10.1016/0022-328X(84)80609-9
Raffaello Romeo, Antonio Grassi, Luigi Monsu Scolaro, Factors affecting reaction pathways in nucleophilic substitution reactions on platinum(II) complexes: a comparative kinetic and theoretical study Inorganic Chemistry. ,vol. 31, pp. 4383- 4390 ,(1992) , 10.1021/IC00047A028
Per E. M. Siegbahn, Robert H. Crabtree, Modeling the Solvent Sphere: Mechanism of the Shilov Reaction Journal of the American Chemical Society. ,vol. 118, pp. 4442- 4450 ,(1996) , 10.1021/JA9541894
Ayusman Sen, Mark A. Benvenuto, Minren Lin, Alan C. Hutson, Naomi Basickes, Activation of Methane and Ethane and Their Selective Oxidation to the Alcohols in Protic Media Journal of the American Chemical Society. ,vol. 116, pp. 998- 1003 ,(1994) , 10.1021/JA00082A022
Kevin L. Bartlett, Karen I. Goldberg, Weston Thatcher Borden, A Computational Study of Reductive Elimination Reactions to Form C−H Bonds from Pt(II) and Pt(IV) Centers. Why Does Ligand Loss Precede Reductive Elimination from Six-Coordinate but Not Four-Coordinate Platinum? Journal of the American Chemical Society. ,vol. 122, pp. 1456- 1465 ,(2000) , 10.1021/JA9915706
Shannon S. Stahl, Jay A. Labinger, John E. Bercaw, Homogeneous Oxidation of Alkanes by Electrophilic Late Transition Metals Angewandte Chemie International Edition. ,vol. 37, pp. 2180- 2192 ,(1998) , 10.1002/(SICI)1521-3773(19980904)37:16<2180::AID-ANIE2180>3.0.CO;2-A
Shannon S. Stahl, Jay A. Labinger, John E. Bercaw, FORMATION AND REDUCTIVE ELIMINATION OF A HYDRIDOALKYLPLATINUM(IV) INTERMEDIATE UPON PROTONOLYSIS OF AN ALKYLPLATINUM(II) COMPLEX Journal of the American Chemical Society. ,vol. 117, pp. 9371- 9372 ,(1995) , 10.1021/JA00141A037
Lars Johansson, Olav B. Ryan, Christian Rømming, Mats Tilset, Redox Chemistry of Dimethylplatinum(II) Diimine Complexes. Oxidatively Induced Pt−Me Transfer between Transient Platinum(III) Cation Radicals Organometallics. ,vol. 17, pp. 3957- 3966 ,(1998) , 10.1021/OM9801498
Hanne Heiberg, Ole Swang, Olav B. Ryan, Odd Gropen, C−H Activation at a Cationic Platinum (II) Center: A Quantum Chemical Investigation Journal of Physical Chemistry A. ,vol. 103, pp. 10004- 10008 ,(1999) , 10.1021/JP992484V