115981-45-8Relevant articles and documents
Large kinetic isotope effects for the protonolysis of metal-methyl complexes are not reliable mechanistic indicators
Scott, Valerie J.,Labinger, Jay A.,Bercaw, John E.
, p. 4374 - 4378 (2011)
Earlier work on protonolyses of several palladium and platinum methyl complexes (with release of methane) had suggested the possibility that observation of an unusually large kinetic isotope effect, consistent with significant contributions from quantum mechanical tunneling, might be diagnostic of a mechanism involving direct protonation of the metal-methyl bond, as opposed to one proceeding via a metal hydride intermediate. By extension of these measurements to a wider set of complexes, we find no support for the proposed correlation.
Preparation and properties of new methyl(alkoxo)- and methyl(thiolato)nickel and methyl(alkoxo)- and methyl(thiolato)palladium complexes. CO and CS2 insertion into the alkoxo-palladium bond
Kim, Yong-Joo,Osakada, Kohtaro,Sugita, Kouji,Yamamoto, Takakazu,Yamamoto, Akio
, p. 2182 - 2188 (2008/10/08)
Reactions of fluorinated alcohols (HOCH(CF3)2, HOCH2CF3, and HOCH(CF3)C6H5) or aromatic thiols (HSC6H5 and HSC6H4-p-CH3) with dialkylnickel and -palladium complexes (NiMe2(bpy), NiEt2(bpy) (bpy = 2,2′-bipyridine), NiMe2(dpe), and PdMe2(dpe) (dpe = 1,2-bis(diphenylphosphino)ethane)) give the corresponding monoalkyl complexes with an alkoxo or a thiolato ligand (NiMe(OR)(bpy), NiEt(OR)(bpy), MMe(OR)(dpe), and MMe(SAr)(dpe) (M = Ni, Pd; R = CH(CF3)2, CH2CF3, CH(CF3)C6H5)). These complexes have been characterized by elemental analysis and NMR (1H, 31P{1H}, 19F, and 13C{1H}) spectroscopy. The methyl(alkoxo)nickel(II) and -palladium(II) complexes thus obtained react with carbon monoxide at normal pressure to give carboxylic esters in high yields. Reaction of carbon monoxide with NiMe(SAr)(dpe) (Ar = C6H5, C6H4-p-CH3) also gives the corresponding carbothioic esters in good yields, while PdMe(SPh)(dpe) is unreactive with carbon monoxide under similar conditions. The 31P{1H} and 13C{1H} NMR spectra of the reaction mixture of PdMe(OCH(CF3)2)(dpe) with an equimolar amount of 13CO at -60°C show the formation of PdMe (13COOCH(CF3)2)(dpe) produced through insertion of the carbon monoxide into the Pd-O bond. When the reaction temperature is raised to -20°C, this alkoxycarbonyl complex undergoes reductive elimination to give 1,1,1,3,3,3-hexafluoro-2-propyl acetate. The reaction is accompanied by simultaneous decarbonylation of the alkoxycarbonyl ligand to regenerate PdMe(OCH(CF3)2)(dpe). The reaction of PdMe(OCH(CF3)Ph)(dpe) with carbon disulfide gives an isolable palladium complex, PdMe(SCSOCH(CF3)Ph)(dpe), formed by insertion of CS2 into the Pd-O bond, while PdMe(SPh)(dpe) is unreactive with CS2.