PX3-induced migratory insertion reactions of half-sandwich-type carbenerhodium(I) complexes

Autor:	Olaf Gevert, Rita Guerrero Sanchez, Helmut Werner, Ulrich Herber, Matthias Laubender
Rok vydání:	2001
Předmět:	Stibine Stereochemistry Ligand Migratory insertion General Chemistry Cleavage (embryo) Medicinal chemistry Catalysis chemistry.chemical_compound Sandwich type chemistry Cyclopentadienyl complex Yield (chemistry) Materials Chemistry
Zdroj:	New Journal of Chemistry. 25:396-399
ISSN:	1369-9261 1144-0546
DOI:	10.1039/b008601k
Popis:	The carbenerhodium(I) complexes trans-[RhCl(CPh2)(L)2] (L = PPri3, 1a; SbPri3, 1b) react with PF3 by cleavage of the rhodium–carbene bond to give the corresponding PF3 derivatives trans-[RhCl(PF3)(L)2] 5a,b, in good yield. In contrast, treatment of the half-sandwich-type compound [(η5-C5H5)Rh(CPh2)(PPri3)], 2a, with both PF3 and P(OPh)3 leads to the migratory insertion of the CPh2 unit into one of the cyclopentadienyl C–H bonds to form the ring-substituted products [{η5-C5H4(CHPh2)}Rh(PX3)(PPri3)] (X = F, 6a; OPh, 6b). The molecular structures of 6a and 6b have been determined by X-ray crystallography. The reaction of the stibine complex [(η5-C5H5)Rh(CPh2)(SbPri3)], 2b, with PF3 proceeds by ligand displacement to afford the new carbenerhodium(I) compound [(η5-C5H5)Rh(CPh2)(PF3)], 7. The mechanism of the migratory insertion reaction is discussed.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::77d8128e3a22bb37253f74e2f63c49ab https://doi.org/10.1039/b008601k Zobrazit plný text záznamu