Молекулярный дизайн катализаторов и катализ в Ð¿Ñ€Ð¾Ñ†ÐµÑÑÐ°Ñ ...

Êîìïëåêñ (1) â êîìáèíàöèè ñ ìåòèëàëþìîêñàíîì (ÌÀÎ) ïîêàçàë
âûñîêóþ êàòàëèòè÷åñêóþ àêòèâíîñòü â ïðîöåññå îëèãîìåðèçàöèè ýòèëåíà
(Òàáëèöà 1), êîòîðàÿ íàìíîãî ïðåâîñõîäèò êàòàëèòè÷åñêóþ àêòèâíîñòü
ïîäîáíûõ èìèííûõ êàòàëèçàòîðîâ òèïà Áðóêõàðòà 3 .
Òàáëèöà 1. Îëèãîìåðèçàöèÿ ýòèëåíà ñ èñïîëüçîâàíèåì êîìïëåêñîâ 1 è 2 a
¹ Ýêñïåðèìåíò
b
Êîìïëåêñ
êîëè÷åñòâî
(ìêìîëü)
MAO
(ýêâ.)
P
(àòì.)
T èñõ ∆T (°C) TOF c,d α c,e α-îëåôèíû
(°C) (× 10 -3 )
c
(%)
1 A 1 12 300 5 25 15 82.5 0.36 31
2 A 1 12 300 12 24 17 87.3 0.37 39
3 A 1 12 300 20 24 19 89.2 0.37 45
4 f A 1 12 300 5 25 14 73.0 0.38 33
5 B 1 1.2 3000 5 24 4 66.2 0.40 38
6 A 2 12 300 5 24 8 33.6 0.43 35
a Óñëîâèÿ ðåàêöèè: 100 ìë òîëóîë, 15 ìèí. b Óñëîâèÿ ýêñïåðèìåíòà.
c Îïðåäåëåíî ìåòîäîì ãàçîâîé õðîìàòîãðàôèè (C 14 /C 16 ). d Ìîëü C 2 H 4 /(ìîëü
Ni × ÷àñ) -1 . e Ïàðàìåòð Øóëüöà-Ôëîðè α = ñêîðîñòü ðîñòà/(ñêîðîñòü ðîñòà +
ñêîðîñòü ïåðåäà÷è öåïè) = ìîëü C n+2 /ìîëü C n . f  ïðèñóòñòâèè 0.01 ìîëü
n-óíäåöåíà.
Ýëåêòðîõèìè÷åñêèé ìåòîä ïîçâîëÿåò ñåëåêòèâíî è â ìÿãêèõ óñëîâèÿõ
ïîëó÷àòü ðàçëè÷íûå òèïû ìåòàëëîîðãàíè÷åñêèõ êîìïëåêñîâ, ñîäåðæàùèõ
ñèãìà-ñâÿçè ìåòàëë-óãëåðîä, ÿâëÿþùèõñÿ âûñîêîýôôåêòèâíûìè
êàòàëèçàòîðàìè ïðîöåññîâ îëèãîìåðèçàöèè è ïîëèìåðèçàöèè
íåíàñûùåííûõ ñîåäèíåíèé.
Ðàáîòà âûïîëíåíà ïðè ôèíàíñîâîé ïîääåðæêå Ñîâìåñòíîé ïðîãðàììû
ôîíäà CRDF è Ìèíèñòåðñòâà îáðàçîâàíèÿ Ðîññèè "Ôóíäàìåíòàëüíûå
èññëåäîâàíèÿ è âûñøåå îáðàçîâàíèå" (Research and Educational Center of
KSU, REC 007), Íåìåöêîãî íàó÷íî-èññëåäîâàòåëüñêîãî îáùåñòâà (DFG,
¹ 436 RUS 17/53/03) è Àêàäåìèè Íàóê Ðåñïóáëèêè Òàòàðñòàí (07-7.1-228)
Ëèòåðàòóðà
1. Technology Vision 2020. The U.S. Chemical Industry, American Chemical
Society, 1996, p. 75; Ä.Ã. ßõâàðîâ, Þ.Ã. Áóäíèêîâà, Î.Ã. Ñèíÿøèí.
Ýëåêòðîõèìèÿ 2003, 39, 1407.
2. A. Held, F.M. Bauers, S. Mecking, J. Chem. Soc., Chem. Commun., 2000, 301.
C. Geyer, S. Schindler, Organometallics 1998, 17, 4400; P.T. Matsanuga, J.C.
Mavrapoulos, C.R. Hess, G.L. Hillhouse, Polyhedron 1995, 14, 175.
3. C.M. Kilian, L.K. Johnson, M. Brookhart, Organometallics 1997, 16, 2005.
98