Areneruthenium(II) complexes with functionalized phosphines coordinating as mono-, bi- or tridentate ligands

Areneruthenium(II) compounds [Ru(p-cym)Cl-2{kappa -P-(PrP)-Pr-i(CH2CH2OMe)( 2)}]. 3. and [Ru(arene)Cl-2{kappa -PRP(CH2CO2Me)(2)}] 4-7 (arene=p-cym (=1- methyl-4-isopropylbenzene). mes (=1,3.5-trimethylbenzene); R = Pr-i, Bu-t) were prepared from the dimers [ Ru(arene)Cl-2](2) and the corresponding fun ctionalized phosphino. Treatment of 6 and 7 with 1 equiv. of AgPF6 affords the monocationic complexes [Ru(mes)Cl{kappa (2)-P,O-RP(CH2C(O)OMe)(CH2CO2Me )}], 10 and 11. while the related reaction of 5-7 with 2 equiv. of AgPr6 pr oduces the dicationic compounds [Ru(p-cym){kappa (3)-P,O,O-(BuP)-Bu-t(CH2C( O)OMe)(2)}](PF6)(2) (12) and [Ru(mes)-{kappa (3)-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){kappa (2)-PO-RP(CH2C(O)OMe)(CH2CO 2Me)}(kappa -O-O2PF2)]PF6. 15- 17, of which 17 (arene = mes; R = Bu-t) has been characterized by X-ray crystallography, Compounds 13 and 14 react with 2 equiv. of (KOBu)-Bu-t in (BuOH)-Bu-t/toluene to give the unsymmetrical c omplexes [Ru(mes){kappa (3)-P,C,O-RP-(CHCO2Me)(CH=C(O)OMe)}], 18 and 19, co ntaining both a five-membered phosphinoenolate and a three-membered phosphi nomethanide ring, The molecular structure of compound 18 has been determine d by X-ray structure analysis. The neutral bis(carboxylate)phosphanidoruthe nium(II) complexes [Ru(arene){kappa (3)-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 (KOBu)-Bu-t and basic Al2O3. Novel tripodal chelating systems ar e generated via insertion reactions of 19 with PhNCO and PhNCS.