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Control of HC(sp 3 ) Bond Cleavage Stoichiometry: Clean Reversible Alkyl Ligand Exchange with Alkane in [LPt(Alk)(H) 2 ] + (L=[2.1.1]‐(2,6)‐Pyridinophane)
Author(s) -
Vedernikov Andrei N.,
Caulton Kenneth G.
Publication year - 2002
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/1521-3773(20021104)41:21<4102::aid-anie4102>3.0.co;2-#
Subject(s) - stoichiometry , alkyl , alkane , cleavage (geology) , chemistry , ligand (biochemistry) , bond cleavage , medicinal chemistry , stereochemistry , crystallography , hydrocarbon , organic chemistry , materials science , catalysis , receptor , biochemistry , fracture (geology) , composite material
Reversible alkane oxidative addition occurs to transient [LPtH] + (L=[2.1.1]‐(2,6)‐pyridinophane; see scheme), which is generated at 86 °C from [LPtMe(H) 2 ] + in 1:1 hydrocarbon/CD 2 Cl 2 mixtures. DFT calculations reveal why [LPtMe(H) 2 ] + eliminates methane, not dihydrogen, and why, in contrast to [LPtMe 2 H] + , no alkane dehydrogenation occurs.