Synthesis and Reactivity of Rhodium Mono- and Bis(diolefin) Complexes. Characterization of Intermediates in the Rhodium-Catalyzed Cyclotetramerization of Butadiene
作者:Marco Bosch、Helmut Werner
DOI:10.1021/om100554d
日期:2010.11.8
[Rh(η3:η3-C8H12)(PR3)]B(Arf)4. The two isomers [Rh(η4-C4H6)2(PR3)]CF3SO3 and [Rh(η3:η3-C8H12)κ1-OS(O)2CF3}(PR3)] are likely intermediates in the (cyclo)oligo- and polymerization of butadiene catalyzed by 1/PR3. While the oligomeric fraction predominantly consists of C12 and C16 olefinic hydrocarbons, the main component among the C16 tetramers is cis,cis,trans,trans-1,5,9,13-cyclohexadecatetraene.
铑双一般组成的(二烯烃)复合物的[Rh(η 4 -二烯)2(L)] X(二烯=丁二烯,异戊二烯,2,3-二甲基,L = P我镨3,PCY 3,P吨卜2 Me,As i Pr 3,Sb i Pr 3,CO,CN t Bu,CN-2,6-C 6 H 3 i Pr 2; X = CF 3 SO 3,B(Ar f)4)由该非离子化合物的[Rh μ-O 2 S(O)CF 3 }(η2 -C 8 ħ 14)2 ] 2(1)和铑[Rh κ 1 -OS(O)2 CF 3 }(η 4 -二烯)2 ](2 - 4)作为前体。的反应1与1,3-环己二烯导致的形成[(η 6 -C 6 H ^ 6)(η的Rh 4 -C 6 H ^ 8)] CF 3 SO 3,而从1和6,6'-二甲基亚甲基不对称夹心化合物[η 5-C 5 ħ 4 CH(CH 3)2 } 铑η 5 -C 5 H ^ 4(= CHÇ 2)CH 3