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Rearrangements versus ligand exchange reactions of organocobalt polymer having cobaltacyclopentadiene moieties in the main chain
Author(s) -
Tomita Ikuyoshi,
Nishio Akinori,
Endo Takeshi
Publication year - 1998
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/(sici)1099-0739(199810/11)12:10/11<735::aid-aoc780>3.0.co;2-l
Subject(s) - chemistry , tetrahydrofuran , polymer chemistry , polymer , ligand (biochemistry) , thermogravimetric analysis , triphenylphosphine , chloroform , thermal stability , tacticity , dimethylformamide , cyclopentadienyl complex , solvent , organic chemistry , polymerization , catalysis , biochemistry , receptor
The rearrangement reaction of an organocobalt polymer with cobaltacyclopentadiene moieties in the main chain ( 1 ) was carried out to yield anew polymer bearing (η 5 ‐cyclopentadienyl) (η 4 ‐cyclobutadiene)cobalt moieties in the main chain ( 2 ). For instance, a polymer (2) containing pure η 4 ‐cyclobutadienecobalt units was obtained as a yellow powder in 79% yield by the reaction of 1 in tetrahydrofuran (THF) at 110 °C for 1 h in a sealed tube. The polymer ( 2 ) obtained was soluble in organic solvents such as chloroform, THF and N , N ‐dimethylformamide and was quite stable under air. It showed good thermal stability and a weight loss of 5% was observed at 482 °C by thermogravimetric analysis (TGA). On the other hand, displacement of the triphenylphosphine ligands on the main chain of the organocobalt polymer ( 1 ), without rearrangement of the cobaltacyclopentadiene rings, was observed when the reaction was carried out in the presence of appropriate ligands such as P(n‐Bu) 3 . The resulting ligand‐exchanged polymer showed different properties in comparison with 1 . For instance a polymer bearing tri‐n‐octylphosphine is soluble in n‐hexane, which is a poor solvent for 1 . © 1998 John Wiley & Sons, Ltd.