16165-95-0Relevant articles and documents
Efficient zirconocene-coupling of silicon-substituted diynes to polymers and macrocycles
Mao, Shane S. H.,Liu, Feng-Quan,Tilley, T. Don
, p. 1193 - 1206 (1998)
The zirconocene-coupling of diynes with internal silicon substituents, MeC≡CMe2SiArSiMe2C≡CMe (1: Ar = 1,4-C6H4; 2: Ar = 1,3-C6H4; 3: Ar = 1,3-C6H4; 3: Ar = 4,4'-C6H4C6H4), generates regiospecific polymers containing zirconacyclopentadiene in the main chain (5-7). These organometallic polymers hydrolyze cleanly to butadienediyl polymers of the type [Me2SiArSiMe2CH = CMeCMe = CH](n) (11-13), and polymer 5 reacts with iodine to give the iodine-containing polymer [1,4-Me2SiC6H4SiMe2C(I)=CMeCMe=C(I)](n) (14). The organometallic polymers undergo facile and high-yield degradations to macrocycles under mild conditions (refluxing tetrahydrofuran solution). The size and shape of the resulting macrocycles depend upon the nature of the diyne spacer group. Thus, polymers 5 and 7 containing parallel diyne units convert to the trimeric macrocycles [Me2SiArSiMe2C4Me2ZrCp2]3 (15: Ar = 1,4-C6H4; 24: Ar = 4,4'- C6H4C6H4), while polymer 6 gives the dimeric macrocycle [1,3- Me2SiC6H4SiMe2C4Me2ZrCp2]2 (18). The dimeric macrocycle [Me2SiC6H4SiMe2C6H4SiMe2C4Me2ZrCp2]2 (20) was obtained directly from the zirconocene coupling of Me2Si[(1,4-C6H4)- SiMe2(C≡CMe)]2 (4) by heating the reaction mixture to reflux. In a similar manner, the diyne Me2Si(C≡CMe)2 was converted in high yield to the hexameric macrocycle [Me2SiC4Me2ZrCp2]6 (22). The macrocycles 15, [1,4-Me2SiC6H4SiMe2C4Me2H2]3 (16), and 18 were characterized by single-crystal X-ray crystallography. Molecules of 15 adopt a nearly planar C3 macrocyclic structure with a cavity described by an average transannular Si···Si distance of 13.2 A?, while the hydrolyzed macrocycle 16 has a chair conformation. This conformation change results from conversion of cis diene groups in the zirconacyclopendiene fragments to trans diene groups in 16. The high- yield formation of macrocycles apparently results from the reversible nature of the alkyne-coupling reaction, which allows for a low-energy pathway to the smallest macrocycle possessing minimal ring strain.
Silicon-containing polymer, process for preparing the same and monomer thereof
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, (2008/06/13)
A silicon-containing polymer comprising a structural unit of the formula (1): wherein R1and R2are the same or different and represent a monovalent organic group having 1 to 20 carbon atoms, and the benzene ring may have a substituent
