246265-71-4Relevant academic research and scientific papers
Investigation of the reactivity of the phosphorus-hydrogen bond in Cp′RuL1L2Cl complexes with diphenylphosphine ligands
Torres-Lubian, Roman,Rosales-Hoz, M. Jesus,Arif, Atta M.,Ernst, Richard D.,Paz-Sandoval, M. Angeles
, p. 68 - 82 (1999)
Products resulting from the oxidation, chlorination, hydrolysis and ethanolysis of Cp*Ru(PHPh2)2Cl (1) are described. Chlorination of the P-H bond in 1 allowed isolation of Cp*Ru(PClPh2)2Cl (6) and there is spectroscopic evidence for the presence of Cp*Ru(PClPh2)(PHPh2)Cl (5). Hydrolysis of compounds 1 and 5 gave a dihydride complex [Cp*Ru(H)2(OPPh2)(POHPh2)] (13) and cationic species [Cp*Ru(PHPh2)3]Cl (14) and [Cp*RuPOHPh2(PHPh2)2]Cl (15). Formation of 14 was confirmed by the synthesis of [Cp*Ru(PHPh2)3]OTf (14′) through intermediate [Cp*Ru(MeCN)(PHPh2)2]OTf (16) which was obtained from the addition of AgOTf to 1 in MeCN solution. Reaction of (Cp*RuCl2)2 (12) in EtOH with two equivalents of PHPh2 gave compound 1 and ethanolysis products Cp*Ru(POEtPh2)(PHPh2)Cl (18) and Cp*Ru(POEtPh2)2Cl (11), while reaction of 12 with diphenylphosphine oxide (OPHPh2) led to the formation of Cp*Ru(POHPh2)2Cl (7), which can either be converted to hydride compound Cp*Ru(H)(Cl)[(OPPh2)(POHPh2)] (10) or an aromatic ring of its coordinated phosphine will bind to the electrophilic [Cp*Ru]+ fragment to give compound [Cp*Ru[μ-(η6-C6H 5)POHPh]Cp*Ru(POHPh2)Cl]Cl (8). Based on 1H- and 31P-NMR spectroscopic data, compounds with two different P-donor ligands have also been prepared, including Cp*Ru(POHPh2)(PHPh2)Cl (9), [Cp*Ru(POHPh2)2(PHPh2)]OTf (17) and Cp*Ru(POHPh2)(POEtPh2)Cl (19). According to NMR observations, a free radical mechanism is proposed for the chlorination and oxidation reactions. Crystal structures are provided for complexes 6, 13 and 18, and a related cationic Cp complex [CpRu(POHPh2)(PHPh2)2]Cl (20).
