Boreskov Institute of Catalysis of the Siberian Branch of Russian ...

PP-I-18NEW OSCILLATING REACTIONS OF ALKYNES CARBONYLATIONCATALYZED WITH Pd COMPLEXESGorodsky S.N., Temkin O.N.M.V. Lomonosov State Academy of Fine Chemical Technology,Vernadsky av. 86, 119571 Moscow, Russia,Phone: (495)936-89-04; Fax: (495)434-87-11; E-mail: Gorodsky@yandex.ruThe oscillating reactions were discovered in many chemical and biological systems. Themost part of oscillatory homogeneous reactions investigated in chemistry are processes oforganic substrate oxidation by strong oxidants. Our team has discovered the criticalphenomena in typical reactions of the organometallic catalysis in which synthesis of complexmolecules occurs. So, the reactions (1, 2) proceed in the system PdBr 2 – KBr – HBr – BuOH–dimethylsulphoxide:2CO + C 2 H 2 + 2BuOH + (CH 3 ) 2 SO ⎯→ BuOCOCH=CHCOOBu (E, Z) + (CH 3 ) 2 S + H 2 O (1)CO + (CH 3 ) 2 SO ⎯→ CO 2 + (CH 3 ) 2 S (2)with periodic change of carbon monoxide and acetylene consumption rate, values of platinumelectrode potential (E Pt ), pH and color of the reaction solution [1]. Oscillations of E Pt and pHwere found out [2] during the study of various alkynes oxidative carbonylation reactions inthe system PdI 2 - KI - MeOH (reaction 3)RC≡CH + 2CO + 2MeOH + ½ O 2 ⎯→ MeOCOC(R)=CHCOOMe (E, Z) + H 2 O (3)where R: Ph, Me, C(CH 3 ) 2 OH. Oxidation CO to СО 2 in this system occurs also. It was thefirst example of oscillating process including the complex molecules synthesis occurs on thebase of relatively simple reagents using (Fig. 1)E( pt), mV16012080400-40-800 20 40 60 80 100 120Т(min)(a)pH5,55,04,54,03,53,02,52,01,50 20 40 60 80 100 120Т(min)(b)Fig. 1. The change of E Pt (a) and pH (b) in the contact solution during of phenylacetylene oxidative carbonylationreaction; KI(0,4 M) – PdI 2 (0,01 M) – PhC≡CH(0,1 M) – CO(60% v.) – O 2 (40% v.)244