158019-92-2Relevant articles and documents
Chelating and hemilabile properties of β- and γ-keto phosphines: (η6-Arene)ruthenium(II) derivatives from γ-keto phosphines and synthesis and reactivity of bis(η2-keto phosphine-P,O)ruthenium(II) complexes
Demerseman, Bernard,Le Lagadec, Ronan,Guilbert, Bénédicte,Renouard, Corinne,Crochet, Pascale,Dixneuf, Pierre H.
, p. 2269 - 2283 (2008/10/08)
The addition of the Ph2P- anion to α,β-enones followed by hydrolysis, provides a convenient synthesis of γ-keto phosphines. The coordination of the γ-keto phosphines, 1, at an (η6-arene)-RuCl2 fragment affords neutral complexes (η6-arene)(η1-keto phosphine-P)RuCl2, 2. The formation of the cationic derivatives [(η6-arene)(η2-keto phosphine-P,O)RuCl]+, 3, is related to the structure of the functional ligand, as specified by the study of the competitive coordination of dimethyl sulfide vs the keto function. The replacement of the arene ligand in (η6-arene)-(L)Ru(X)Cl [X = Cl; L = PMe3, PPh3, P(OMe)3 or LX = phosphino enolato] complexes with β-keto phosphines occurs in methanol. The removal of both the arene and chloride ligands allows the coordination of two molecules of β-keto phosphine and results in the cationic derivatives [(η2-keto phosphine-P,O)2(L)RuCl]+, 5, and [(η2-keto phosphine-P,O)2(η2-phosphino enolato-P,O)Ru]+, 6, isolated as their (PF6)- salts. The substitution of the arene by carbon monoxide and one molecule of β- or γ-keto phosphine, results in the formation of the neutral (η2-keto phosphine-P,O)(η2-phosphino enolato-P,O)(CO)RuCl complexes, 7. Starting from [(η6-arene)-RuCl2]2 precursors, the removal of the arene by keto phosphines provides access to the neutral complexes (η2-keto phosphine-P,O)2RuCl2, 9, with cis phosphorus and trans chlorine atoms. The coordination of carbon monoxide on complexes 9 involves the hemilabile property of the keto phosphine ligands and leads to derivatives (η2-keto phosphine-P,O)(η1-keto phosphine-P)(CO)RuCl2, 10, with trans phosphorus atoms. The methanol induced cleavage of one ruthenium chlorine bond in complexes 9 and subsequent coordination of a nitrile or phenylacetylene afford the complexes [(η2-keto phosphine-P,O)2(RC≡N)RuCl](PF6), 14, and {[η2-Ph2PC(Me)2CH 2C-(Me)=O-P,O]2(PhCH=C=)RuCl}(PF6), 15, where the cis arrangement of the phosphorus atoms is retained. The phosphino enolato complexes [η2-Ph2PCH=C(But)O-P,O] 2(CO)2Ru, 16, with trans phosphorus and trans carbon monoxide, and [η2-Ph2PC(R)=C(But)O-P,O] 2(MeC≡N)2- Ru, 17, with cis phosphorus and trans acetonitrile, were obtained under mild basic conditions from complexes 9 incorporating enolizable β-keto phosphines.
