Cyclometalated and NNN Terpyridine Ruthenium Photocatalysts and Their Cytotoxic Activity.

The cyclometalated terpyridine complexes [Ru(η-OAc)(NC-tpy)(PP)] (PP = dppb , (,)-Skewphos , (,)-Skewphos ) are easily obtained from the acetate derivatives [Ru(η-OAc)(PP)] (PP = dppb, (,)-Skewphos , (,)-Skewphos ) and tpy in methanol by elimination of AcOH. The precursors , are prepared from [Ru(η-OAc)(PPh)] and Skewphos in cyclohexane. Conversely, the NNN complexes [Ru(η-OAc)(NNN-tpy)(PP)]OAc (PP = (,)-Skewphos , (,)-Skewphos ) are synthesized in a one pot reaction from [Ru(η-OAc)(PPh)], PP and tpy in methanol.

Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds.

The cationic achiral and chiral terpyridine diphosphine ruthenium complexes [RuCl(PP)(tpy)]Cl (PP=dppp (1), (R,R)-Skewphos (2) and (S,S)-Skewphos (3)) are easily obtained in 85-88 % yield through a one-pot synthesis from [RuCl (PPh ) ], the diphosphine and 2,2':6',2''-terpyridine (tpy) in 1-butanol. Treatment of 1-3 with NaPF in methanol at RT affords quantitatively the corresponding derivatives [RuCl(PP)(tpy)]PF (PP=dppp (1 a), (R,R)-Skewphos (2 a) and (S,S)-Skewphos (3 a)). Reaction of [RuCl (PPh ) ] with (S,R)-Josiphos or (R)-BINAP in toluene, followed by treatment with tpy in 1-butanol and finally with NaPF in MeOH gives [RuCl(PP)(tpy)]PF (PP=(S,R)-Josiphos (4 a), (R)-BINAP (5 a)) isolated in 78 % and 86 % yield, respectively.

Enantioselective Cytotoxicity of Chiral Diphosphine Ruthenium(II) Complexes Against Cancer Cells.

The chiral cationic complex [Ru(η -OAc)(CO)((R,R)-Skewphos)(phen)]OAc (2 ), isolated from reaction of [Ru(η -OAc)(η -OAc)(R,R)-Skewphos)(CO)] (1 ) with phen, reacts with NaOPiv and KSAc affording [RuX(CO)((R,R)-Skewphos)(phen)]Y (X=Y=OPiv 3 ; X=SAc, Y=OAc 4 ). The corresponding enantiomers 2 -4 have been obtained from 1 containing (S,S)-Skewphos. Reaction of 2 and 2 with (S)-cysteine and NaPF at pH=9 gives the diastereoisomers [Ru((S)-Cys)(CO)(PP)(phen)]PF (PP=(R,R)-Skewphos 2 -Cys; (S,S)-Skewphos 2 -Cys).

Preparation of Neutral [Ru(OCR)P(NN)], Cationic [Ru(OCR)P(NN)](OCR) and Pincer [Ru(OCR)(CNN)P] (P = PPh, P = diphosphine) Carboxylate Complexes and their Application in the Catalytic Carbonyl Compounds Reduction.

The diacetate complexes -[Ru(κ-OAc)(PPh)(NN)] (NN = ethylenediamine (en) (), 2-(aminomethyl)pyridine (ampy) (), 2-(aminomethyl)pyrimidine (ampyrim) ()) have been isolated in 76-88% yield by reaction of [Ru(κ-OAc)(PPh)] with the corresponding nitrogen ligands. The ampy-type derivatives and undergo isomerization to the thermodynamically most stable cationic complexes [Ru(κ-OAc)(PPh)(NN)]OAc ( and ) and -[Ru(κ-OAc)(PPh)(NN)] ( and ) in methanol at RT. The -[Ru(κ-OAc)(P)] (P = dppm (), dppe ()) compounds have been synthesized from [Ru(κ-OAc)(PPh)] by reaction with the suitable diphosphine in toluene at 95 °C.

Cationic carboxylate and thioacetate ruthenium(ii) complexes: synthesis and cytotoxic activity against anaplastic thyroid cancer cells.

The cationic acetate ruthenium complex [Ru(η1-OAc)(CO)(dppb)(phen)]OAc (1) is easily prepared in 83% yield from [Ru(η1-OAc)(η2-OAc)(CO)(dppb)] (dppb = 1,4-bis(diphenylphosphino)butane) and 1,10-phenanthroline (phen) in MeOH. The derivative 1 undergoes easy substitution of the coordinated acetate by reaction with NaOPiv, KSAc, and KSCN in MeOH, affording the corresponding complexes [RuX(CO)(dppb)(phen)]X (X = OPiv, 2; SAc, 3; and NCS, 4), whereas its reaction with NaCl and NH4PF6 affords [RuCl(CO)(dppb)(phen)]PF6 (5). Carboxylate complexes 1 and 2 show high solubility in water, enabling easy exchange of the coordinated carboxylate by water and other ligands (CH3CN, glutathione).