344358-05-0Relevant articles and documents
Complexation of unsaturated carbon-carbon bonds in π-conjugated polymers with transition metals
Huber,Bangerter,Caseri,Weder
, p. 3857 - 3863 (2007/10/03)
The present paper explores the possibility of preparing π-conjugated organometallic polymer hybrid systems based on a poly(p-phenylene ethynylene) (PPE) derivative, in which the ethynylene moieties of the polymer are coordinated to platinum(II) centers. The use of the bifunctional [Pt-(μ-Cl)Cl(PhCH=CH2)]2 (2) allows, under appropriate conditions, the formation of three-dimensionally cross-linked, conjugated PPE-platinum(II) networks. The synthesis of [Pt-(μ-Cl)Cl(PhC≡CPh)]2, as a model compound, and a series of model reactions of 2 with diphenylacetylene (3) have enabled an NMR study which has revealed a number of equilibria, and suggests a mixed Pt-styrene-acetylene complex as a key structure. As expected, the coordination of Pt markedly influences the photophysical characteristics of the PPE. The photoluminescence is efficiently quenched, and the absorption maximum in the visible regime experiences a hypsochromic shift upon complexation with 2.
HYDROSILYLATION CHEMISTRY AND CATALYSIS WITH cis-PtCl2(PhCH equals CH2)2.
Caseri,Pregosin
, p. 1373 - 1380 (2008/10/08)
The precursor cis-PtCl//2(PhCH equals CH//2)//2 is shown to catalyze (i) the hydrosilylation of various terminal olefins and acetylenes, (ii) the reduction of carbonyl functions with silanes in the presence of pyridine or aniline as cocatalyst, and (iii) the formation of R//3**1SiOR**2 from R//3**1SiH and R**2OH. The hydrosilylation of styrene is shown to proceed via reduction of PtCl//2(PhCH equals CH//2)//2 to Pt(PhCH equals CH//2)//3 with concomitant formation of 2 equiv of R//3SiCl and 1 equiv of PhCH//2CH//3. Extensive **1**9**5Pt measurements together with **1**3C studies on complexed styrene selectively enriched at the beta -carbon support the formationof the Pt(0) complex. The precursor cis-PtCl//2(PhCH equals CH//2)//2 is suggested to arise from the trans isomer which is identified by **1**9**5Pt NMR and its reaction chemistry.
