from first principles PP-I-1

OP-III-32Solid State Isotope Exchange with Spillover Hydrogenin Organic CompoundsZolotarev Yu.A. 1 , Dadayan A.K. 1 , Borisov Yu.A. 2 , Nazimov I.V. 3 , Vaskovsky B.V. 3 ,Myasoedov N.F. 11 Institute of Molecular Genetics RAS, Moscow, Russia2 Nesmeyanov Institute of Organoelement Compounds RAS, Moscow, Russia3 Shemyakin–Ovchinnikov Institute of Bioorganic Chemistry RAS, Moscow, Russiazolya@img.ras.ruThis report summarizes data on the theoretical and experimental investigation of hightemperature solid state catalytic isotope exchange (HSCIE) that takes place in organiccompounds under the action of spillover hydrogen (SH) [1]. The HSCIE reaction has beenshown to proceed on Brendsted-type acidic centers formed under the action of SH. The newone-center synchronous mechanism of hydrogen substitution in organic compounds has beenstudied. Analysis of the kinetic isotopic effects of the HSCIE reaction were conducted for thefirst time. The dependence of the reaction’ s activation energy on the parameters of acidiccenters type H + (H 2 O) n was established. It was shown that the kinetic isotopic effect of solidstate reaction of hydrogen exchange with SH is 1.2 – 1.4, which is several times lower thanthat of liquid state reactions of protium and deuterium transfer (equal to 3 to 30). Goodagreement was observed between our experimental data and the results of quantum chemicalmeasurements of hydrogen exchange on model acidic centers type H + (H 2 O) n . By using theHSCIE reaction, highly deuterium- and tritium-labeled histamine and melatonine with a70-95% degree of substitution of all C-H bonds were produced. By reaction HSCIE weobtained deuterium-labeled octapeptide bradikinin with 7 atoms of deuterium and labeledhexapeptide dalargin with 14 atoms of deuterium. The HSCIE reaction proceeds in thevirtually complete absence of racemization, that makes this reaction a valuable preparativemethod of the production of evenly tritium or deuterium labeled organic compounds.Complexes of deuterium-labeled histamine with transition metals were obtained, and isotopeeffects in these complexes were studied by electron spectroscopy. Theoretical assessment ofisotopic effect by the electron spectroscopy of the complexes of deuterium-labeled histamineswith metals was performed using RB3LYP/LanL2DZ and CIS/LanL2DZ. As for thecomplexes of histamine with platinum and copper, the isotopic effect in UV-absorptionspectra was 1600 and 1800 cal/mol, respectively.[1] Yu.A. Zolotarev, A.K. Dadayan, Yu.A. Borisov, V.S. Kozik, Chem. Rev., 110, (2010) 5425.76