Abstract
Three new highly hindered triorganoboranes tris(4- t-buthyl-2,6-dimethylphenyl)borane (BDP) 3B), ( 5) tris-(4- t-methoxy-2,6-dimethylphenyl)borane, (DMP) 3B ( 6), and t-butyl bis(2,4,6-trimethylphenyl)borane (Mes 2BBu t) ( 7), were prepared and compared with trimesitylborane ( 4) for their influence on the 1,4-content of anionically produced polymers of butadiene. Each was design to overcome known reactions of ( 4). Unexpectedly, none was more effective overall than ( 4) in increasing the 1,4- content of polymer. Borane( 7) simply quenched LiBu n induced polymerisations, whilst ( 6) and ( 7) somewhat enhanced the 1,4-character and sharpened the polymer profile. However, ( 6) and ( 7) quenched polymerisations by sodium bases. Studies of the reactions of bases with a variety of hindered boranes suggest reasons for the results obtained, and help with the design of other, possibly more effective, catalyst.
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