Bridging the gap between homogeneous and heterogeneous catalysis: ortho/para H(2) conversion, hydrogen isotope scrambling, and hydrogenation of olefins by Ir(CO)Cl(PPh(3))(2).
نویسندگان
چکیده
Some transition metal complexes are known to catalyze ortho/para hydrogen conversion, hydrogen isotope scrambling, and hydrogenation reactions in liquid solution. Using the example of Vaska's complex, we present here evidence by NMR that the solvent is not necessary for these reactions to occur. Thus, solid frozen solutions or polycrystalline powdered samples of homogeneous catalysts may become heterogeneous catalysts. Comparative liquid- and solid-state studies provide novel insight into the reaction mechanisms.
منابع مشابه
Coordination features of a hybrid scorpionate/phosphane ligand exemplified with Iridium.
Although the pentacoordinated complex [Ir{(allyl)B(CH(2)PPh(2))(pz)(2)}(cod)] (1; pz=pyrazolyl, cod=1,5-cyclooctadiene), isolated from the reaction of [{Ir(mu-Cl)(cod)}(2)] with [Li(tmen)][B(allyl)(CH(2)PPh(2))- (pz)(2)] (tmen=N,N,N',N'-tetramethylethane-1,2-diamine), shows behavior similar to that of the related hydridotris(pyrazolyl)borate complex, the carbonyl derivatives behave in a quite d...
متن کاملAt the frontier between heterogeneous and homogeneous catalysis: hydrogenation of olefins and alkynes with soluble iron nanoparticles.
The use of non-supported Fe nanoparticles in the hydrogenation of unsaturated C-C bonds is a green catalytic concept at the frontier between homogeneous and heterogeneous catalysis. Iron nanoparticles can be obtained by reducing Fe salts with strong reductants in various solvents. FeCl(3) reduced by 3 equivalents of EtMgCl forms an active catalyst for the hydrogenation of a range of olefins and...
متن کاملOxidative addition of SiH4 and GeH4 to Ir(PPh3)2(CO)Cl: structural and spectroscopic evidence for the formation of products derived from cis oxidative addition.
X-ray diffraction studies demonstrate that oxidative addition of SiH(4) to Ir(PPh(3))(2)(CO)Cl yields Ir(PPh(3))(2)(CO)(Cl)(SiH(3))H, which features a cis arrangement of the SiH(3) and H ligands in which H is located trans to CO, rather than trans to Cl as originally reported. (1)H NMR spectroscopic studies indicate that oxidative addition of GeH(4) to Ir(PPh(3))(2)(CO)Cl also occurs in a cis m...
متن کاملDesign of the Reactor, Selection of Catalyst for Ortho to Para Hydrogen Conversion and Preliminary Design of Cryogenic System for its Liquefaction
Hydrogen is an unusual substance in that its molecule exists in two forms, known as ortho and para, with markedly different properties. Energy level of the ortho molecule is higher than para, therefore, the latter is employed for industrial purposes. Consequently, for a high conversion of ortho to para hydrogen a catalyst reactor must be employed. Therefore, one of the main obj...
متن کاملSurface-assisted transfer hydrogenation catalysis on a γ-Al2O3-supported Ir dimer.
A novel oxide-supported Ir dimer, which was found to be active for transfer hydrogenation of aromatic ketones, was prepared on a γ-Al(2)O(3) surface from an Ir dimer complex [Ir(2){η(5)-C(5)(CH(3))(5)}(2)(μ-CH(2))(2)] (Ir(2)) with an Ir=Ir bond. Detailed characterization of the γ-Al(2)O(3)-supported Ir dimer (Ir(2)/γ-Al(2)O(3)) revealed that the structure of Ir(2) consisted of an Ir dimer with ...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Journal of the American Chemical Society
دوره 126 27 شماره
صفحات -
تاریخ انتشار 2004