Chemistry of metal hydrides. Part XX. The nature of the insertion rearrangement of acetylenes with platinum(II) hydrides

Autor:	T. G. Attig, H. C. Clark, C. S. Wong
Rok vydání:	1977
Předmět:	Chemical polarity Organic Chemistry Migratory insertion Side reaction chemistry.chemical_element Tricyclohexylphosphine General Chemistry Photochemistry Medicinal chemistry Catalysis Metal Solvent chemistry.chemical_compound chemistry Acetylene visual_art visual_art.visual_art_medium Platinum
Zdroj:	Canadian Journal of Chemistry. 55:189-198
ISSN:	1480-3291 0008-4042
Popis:	The reactions of platinum(II) hydrides, trans-PtHXL2, where X = NO3, Cl or CH3OH, and L = PEt3 or tricyclohexylphosphine, with disubstituted acetylenes, R1C≡CR2 have been examined under a variety of conditions. From spectroscopic parameters, the gross geometry at platinum as well as the geometry of the resulting alkenyl groups in the products have been determined. The observation that all alkenyl groups have a cis geometry is consistent with a migratory insertion step involving a four-centred transition state, in which the disposition of the acetylene relative to the Pt—H bond appears to be dependent on the Pt—H bond polarity. Evidence is presented to demonstrate that this polarity depends on several factors including solvent, and ligands on Pt(II). For L = tricyclohexylphosphine, the occurrence of a side reaction which competes with insertion and which leads to a Pt(0) acetylene complex is also demonstrated, and other interesting reactions are described.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::7924271c80ce6b36d4b8d605f914dce9 https://doi.org/10.1139/v77-032 Zobrazit plný text záznamu