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Reactions of Titanocene Derivatives with Molecular Carboxylic Acids and Copolymers Bearing Carboxylic Acid Groups
Author(s) -
Branham Keith E.,
Mays Jimmy W.,
Gray Gary M.,
Sanner Robert D.,
Overturf George E.,
Cook Robert
Publication year - 1997
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(199703)11:3<213::aid-aoc555>3.0.co;2-o
Subject(s) - chemistry , copolymer , carboxylic acid , benzoic acid , polymer chemistry , methacrylic acid , titanium , styrene , cyclohexanecarboxylic acid , carboxylate , pivalic acid , organic chemistry , polymer , catalysis
Linear, soluble copolymers containing titanium are of interest for use in targets for inertial‐confinement fusion (ICF) experiments because the titanium is a useful spectroscopic probe for studying the nuclear fusion process. We have studied the reactions of dichloro‐ titanocene and diphenyltitanocene with carboxylic acids to determine if these can be used to prepare such polymers. Model reactions of dichlorotitanocene with p ‐toluic acid show that both mono‐ and di‐carboxylates are formed. We have prepared a soluble titanium‐containing copolymer via the reaction of poly(styrene‐ co ‐methacrylic acid) with an excess of dichlorotitanocene but attempts to remove the excess molecular titanocene from the copolymer result in crosslinking of the copolymer. Model reactions of benzoic and pivalic acids with diphenyltitanocene demonstrate that monosubstituted carboxylato(phenyl)titanocenes are formed but that these products are stable only at low temperatures and decompose readily at ambient temperature. Proton NMR studies of the reaction of diphenyltitanocene and benzoic acid at −20 °C indicate that this reaction is second order, suggesting that the reaction does not proceed through a benzyne intermediate. © 1997 by John Wiley & Sons, Ltd.