Ruthenium Complexes with Dithiophosphonates [Ar(RO)PS₂]⁻and [Fc(RO)PS₂]⁻(Ar =p-CH₃OC₆H₄, Fc = Fe(η⁵-C₅H₄)(η⁵-C₅H₅))

Abstract

Treatment of dimeric [(η6-p-cymene)RuCl(μ-Cl)]2 with Lawesson’s reagent [ArP(S)(μ-S)]2 (Ar = p-C6H4OMe) in THF gave [(η6-p-cymene)Ru{μ-η1(S),η2(S,S′)-ArP(S)S2}]2 (1) as the sole isolable product. The chlorides in the starting ruthenium compound were substituted by [ArP(S)S2]2− as a bridging dithiolato ligand. Interactions of [Ru(PPh3)3Cl2] and [RuHCl(CO)(PPh3)3] with Lawesson’s reagent in the presence of ammonium hydroxide gave the dinuclear neutral complexes [Ru(μ-η1(O),η1(S),η1(S,S′)-ArPOS2)(PPh3)2]2 (2) and [Ru(CO)(μ-η1(O),η2(S,S′)-ArPOS2)(PPh3)]2 (3), respectively, in which the [ArPOS2]2− ligands bind the two Ru atoms via both sulfur and oxygen atoms. Reaction of dimeric [Cp*Ru(OMe)]2 (Cp* = η5-C5Me5) with Lawesson’s reagent in the presence of ammonium hydroxide led to isolation of a novel ruthenium(IV) complex, [Cp*Ru{(ArPS2O)2H}] (4). Reaction of [Ru(PPh3)3Cl2] or [RuHCl(CO)(PPh3)3] with Na[FcP(OMe)S2], which was prepared from [FcP(S)(μ-S)]2 (Fc = Fe(η5-C5H4)(η5-C5H5)) and MeONa in methanol, gave the neutral mononulcear complexes cis-[Ru{Fc(OCH3)PS2}2(L′)(PPh3)] (L′ = PPh3 5, CO 6). Interaction of [Ru(PPh3)3Cl2] or [RuHCl(CO)(PPh3)3] with [FcP(S)(μ-S)]2 in the presence of ammonium hydroxide in THF gave [Ru{Fc(OH)PS2}2(L′)(PPh3)] (L′ = PPh3 7, CO 8). Treatment of [(η6-p-cymene)RuCl(μ-Cl)]2 with [FcP(OH)S(SH)] in the presence of excess NaHCO3 led to isolation of [(η6-p-cymene)Ru{η1(S),η2(S,S′)-FcPS2OP(S)SFc}] (9). The crystal structures of 1, 2, 3·CH2Cl2·THF, 4·CH2Cl2·0.5H2O, 6, 7·CH2Cl2·3/4C6H14, and 9·CH2Cl2 along with their spectroscopic properties are reported.

Aquacarbonyl(ferrocenyldithiophosphonato-κ2S,S′)bis(triphenylphosphane-κP)ruthenium(II) dichloromethane monosolvate

“…The [FcP(O)S 2 ] 2acts as a chelating ligand through its two sulfur atoms to bond the ruthenium center with the bite angle S(1) -Ru(1)-S(2) of 79.74 (4)° which agrees with those in cis- [Ru(CO) (Zhang et al, 2001). The Ru-C bond length and Ru-C-O bond angle in the title complex are 1.826 (4) Å and 176.9 (4)°, respectively, which are comparable to those in [Ru(CO){ARP(O)S 2 }(PPh 3 ) 2 ] 2 (Ar = p-C 6 H 4 OMe) (Ru-C = 1.804 (4) Å and Ru-C-O = 174.8 (4)°) (Wang et al, 2010) and [RuH(CO){S 2 P(OEt) 2 }(PPh 3 ) 2 ] (Ru-C = 1.829 (4) Å and Ru-C -O = 175.4 (4)°) (Liu et al 2005).…”

“…For background to ferrocenyl-phosphonodithiolato complexes, see: Foreman et al (1996); Gray et al (2003Gray et al ( , 2004; Haiduc (2001); Thomas et al (2001); Van Zyl (2010). For a related structure, see: Liu et al (2005); Wang et al (2010); Zhang et al (2001). For a description of the Cambridge Structural Database, see: Allen (2002).…”

“…Similarly, [FcP(S)(µ-S)] 2 can undergo a ring opening reaction by nucleophilic attack under suitable conditions, resulting in formation of the typical ferrocenyl-dithiophosphonate ligands, which may directly react with a range of metal ions to produce new heterometallic complexes containing the electron-rich and aromatic ferrocene groups (Gray et al, 2003;Thomas et al, 2001). As a part of research interest to the later transition metal-sulfur chemistry, we have recently reported ruthenium complexes with ferrocenyl-phosphonodithiolate as a dithio ligand (Wang et al, 2010). We here describe the crystal structure of a ruthenium(II)-ferrocenyl-dithiophosphonato complex [{FcP(O)S 2 }Ru(CO)(H 2 O)(PPh 3) 2].CH 2Cl 2 (Fc = Fe(η 5 -C 5 H 4 )(η 5 -C 5 H 5 )) in this paper.…”

Antibacterial Activity of Amidodithiophosphonato Nickel(II) Complexes: An Experimental and Theoretical Approach

“…Compounds (BzNH3)2[Ni(dtp)2]•2H2O (black triangle in Figure 4) and (PhBuNH3)2[Ni(dtp)2] (red triangle in Figure 4) lie in the same region as the anionic fragments. It is worth noting the three blue squares lying in the same region as the yellow dots: these data refer to structures (IKOSUX and LIFGAJ) [10,[33][34][35][36][37][38][39][40] containing single P─OH bonds in neutral fragments, thus confirming the proposed correlation.…”

Heterodimetallic Ferrocenyl Dithiophosphonate Complexes of Nickel(II), Zinc(II) and Cadmium(II) as Sensitizers for TiO2‐Based Dye‐Sensitized Solar Cells

“…FcLR undergoes a ring opening reaction allowing cleavage of the dimer and produced ammonium salt that was isolated as a bright yellow powder. Previously, various groups of alcohols had been used for FcLR, including methanol, ethanol, and isopropanol and ring opening by ammonia hydrate have been reported . A number of ligands through a combination of S/N/O heterocyclic atoms have been used in the nucleophilic ring opening reaction of the FcLR reagent .…”