395682-50-5Relevant academic research and scientific papers
Areneruthenium(II) complexes with functionalized phosphines coordinating as mono-, bi- or tridentate ligands
Werner, Helmut,Bank, Juergen,Windmueller, Bettina,Gevert, Olaf,Wolfsberger, Werner
, p. 3162 - 3177 (2001)
Areneruthenium(II) compounds [Ru(p-cym)Cl2{κ-P-iPrP(CH2CH 2OMe)2}], 3, and [Ru(arene)Cl2{κ-P-RP(CH2CO2Me) 2}] 4-7 (arene = p-cym (= 1-methyl-4-isopropylbenzene), mes (= 1,3,5-trimethylbenzene); R = iPr, ′Bu) were prepared from the dimers [Ru(arene)Cl2]2 and the corresponding functionalized phosphine. Treatment of 6 and 7 with 1 equiv. of AgPF6 affords the monocationic complexes [Ru(mes)Cl{κ2-P,O-RP(CH2C(O)OMe)(CH 2CO2Me)}]PF6, 10 and 11, while the related reaction of 5-7 with 2 equiv. of AgPF6 produces the dicationic compounds [Ru(p-cym){κ3-P,O,O-′BuP(CH2C(O)OMe) 2}](PF6)2 (12) and [Ru(mes){κ3-P,O,O-RP(CH2C(O)OMe)2}] (PF6)2, 13 and 14. Partial hydrolysis of one hexafluorophosphate anion of 12-14 leads to the formation of [Ru(arene){κ2-P,O-RP(CH2C(O)OMe)(CH 2CO2Me)}(κ-O-O2PF2)]PF 6, 15-17, of which 17 (arene = mes; R = ′Bu) has been characterized by X-ray crystallography. Compounds 13 and 14 react with 2 equiv. of KO′Bu in ′BuOH/toluene to give the unsymmetrical complexes [Ru(mes){κ3-P,C,O-RP-(CHCO2Me)(CH=C(O)OMe)}], 18 and 19, containing both a five-membered phosphinoenolate and a three-membered phosphinomethanide ring. The molecular structure of compound 18 has been determined by X-ray structure analysis. The neutral bis(carboxylate)phosphanidoruthenium(II) complexes [Ru(arene){κ3-P,O,O-RP-(CH2C(O)O)2}], 20-23 are obtained either by hydrolysis of 18 and 19, or by stepwise treatment of 4 and 5 with KO′Bu and basic Al2O3. Novel tripodal chelating systems are generated via insertion reactions of 19 with PhNCO and PhNCS.
