209854-68-2

Upstream product

• 12150-46-8 1,1'-bis-(diphenylphosphino)ferrocene 
• 52462-29-0 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 
• 923276-43-1 [RuCl(PPh3)(η1-dppf)(η6-p-cymene)]PF6 
• 52490-94-5 [dichloro(p-cymene)(triphenylphosphane)ruthenium(II)] 

Downstream Products

• 1389343-83-2 [Ru(η6-p-cymene)(1,1'-bis(diphenylphosphino)ferrocene))Cl]SnCl3 
• 1389343-72-9 [Ru(η6-p-cymene)(1,1'-bis(diphenylphosphino)ferrocene))Br]PF6 
• 1389343-77-4 [Ru(η6-p-cymene)(1,1'-bis(diphenylphosphino)ferrocene))I]PF6 

Relevant academic research and scientific papers

Synthesis and characterization of [Ru(η6-C 10H14)(dppf)X][PF6] (X = Cl, Br, I, SnF 3) compounds: The X-ray structure of [Ru(η6-C 10H14)(dppf)Cl][SnCl3]·0.45CH 2Cl2

The arene-ruthenium complex [Ru(η6-C10H 14)(dppf)Cl]PF6 (1) was used as a precursor for the syntheses of the [Ru(η6-C10H14)(dppf)Br] PF6 (2), [Ru(η6-C10H14)(dppf)I] PF6 (3), [Ru(η6-C10H14)(dppf) SnF3]PF6 (4) and [Ru(η6-C 10H14)(dppf)Cl][SnCl3]·0.45CH 2Cl2 (5) complexes by its reactions with KBr, KI, SnF 2 and SnCl2, respectively. All of the compounds were characterized by NMR, IR, 57Fe and 119Sn-Mo?ssbauer spectroscopy, and cyclic voltammetry. The single-crystal X-ray structure analysis of the [Ru(η6-C10H14)(dppf)Cl] [SnCl3]·0.45CH2Cl2 complex revealed the expected piano-stool geometry. Cyclic voltammograms of the complexes showed only one quasi-reversible electrochemical process, involving the oxidation of Fe(II) and Ru(II) at the same potential, which was confirmed by exhaustive electrolysis experiments. 57Fe-Mo?ssbauer parameters obtained for the complexes (1-5) were fitted with one doublet corresponding to a site of one iron(II). The 119Sn-Mo?ssbauer parameters of the complex (4) indicate that tin is tetra covalent.

Ambi-valence taken literally: Ruthenium vs iron oxidation in (1,1′-diphosphinoferrocene)ruthenium(II) hydride and chloride complexes as deduced from spectroelectrochemistry of the heterodimetallic mixed-valent intermediates

Combining two different redox-active organometallic moieties, we prepared the compounds [(Cym)RuCl(dpf)](PF6), with Cym = p-cymene = 1-isopropyl-4-methylbenzene, and the diphosphinoferrocenes (dpf) 1,1′-bis(diphenylphosphino)ferrocene (dppf; complex 3), 1,1′-bis(diisopropylphosphino)ferrocene (dippf; complex 4), and 1,1′-bis(diethylphosphino)ferrocene (depf; complex 5) as well as the structurally characterized hydride complex [(C5Me5) RuH(dippf)] (2). In contrast to the case for 2, with an approximately staggered ferrocene conformation, the chloride complexes 3-5 exhibit a syn-periplanar ferrocene arrangement due to a Cl...H(C5H4) interaction in the solid and in solution. The related new compounds [(Cym)RuH(dppf)](PF6) (6) and trinuclear (μ-dpf)[(Cym)RuCl 2)]2 (7-9) were also obtained and identified by 1H and 31P NMR spectroscopy. The redox behavior of 2-6 and of the known [(C5Me5)RuH(dppf)] (1) was investigated using cyclic voltammetry, spectroelectrochemistry in the UV/vis/near-IR and IR regions, and, in part, by EPR. The first oxidation of the areneruthenium compounds 3-6 occurs reversibly at the ferrocene site, while the reduction proceeds via an ECE two-electron pattern under chloride dissociation. These results are compared to those obtained for the pentamethylcyclopentadienide/ hydride complexes 1 and 2, which demonstrate unambiguously the ruthenium center as the site of the first electron loss. The different results for the two kinds of heterodimetallic d5/d6 mixed-valent intermediates, FeIIRuIII for 1+ and 2+ and Fe IIIRuII for 3+-6+, are discussed with respect to the possible uses of such heterodinuclear systems in H 2 conversion catalysis.

Mechanistic studies on the formation of η2-diphosphine (η6-p-cymene)ruthenium(II) compounds

A new range of pendent diphosphine (η6-p-cymene) ruthenium(II) complexes, [RuCl(PPh3)(η1-(P-P))- (η6-p-cymene)]PF6 (P-P -dppm, cis-PPh 2CHCHPPh2 (dppv), dppe, dppp, dppf), have been prepared by substitution of the labile acetonitrile ligand in [RuCl(CH3CN) (PPh3)(η6-p-cymene)]PF6. The formation of chelate complexes, [RuCl(η2-(P-P))(η6-p-cymene)] +, from these pendent phosphine complexes and from the related neutral complexes, [RuCl2(η1-(P-P))(η6- p-cymene)] (P-P = dppm, dppv), has been investigated, including determination of activation enthalpies (ΔH?) and entropies (ΔS?). A concerted substitution mechanism is proposed for the latter complexes, in which methanol plays an important role in the ring-closing process by formation of hydrogen bonds with the chloride ligands. This proposal is supported by volumes of activation (ΔV?) determined by variable-pressure UV-visible spectroscopy. In contrast, a dissociative mechanism is proposed for the series of cationic pendent phosphine complexes, which generally require higher temperatures to effect ring closure. Secondary reaction pathways can be observed in some cases and are discussed in terms of differences between the phosphine complexes and supplemented by investigations using electrospray ionization mass spectrometry (ESI-MS). The X-ray structures of [RuCl(PPh3) (η1-(P-P))(η6-p-cymene)]PF6 (P-P = dppm, dppv, dppp) and [RuCl(η2-dppv)-(η6-p-cymene) ]PF6 are also reported.

Preparations and structures of (η6-arene)ruthenium(II) complexes bearing 1,1′-bis(diphenylphosphinomethyl)ferrocene or 1,1′-bis(diphenylphosphino)ferrocene

Reactions of bis[dichloro(η6-arene)ruthenium] 1 with 1,1′-bis[(diphenylphosphino)methyl]ferrocene (dpmf) gave the dpmf-P,P′ bridged complexes [(η6-arene)RuCl2]2(μ-dpmf) 2, where arenes=(a) 1,2,3,4-Me4C6H2; (b) C6Me6; (c) p-cymene; (d) 1,2,3,5-Me4C6H2; (e) 1,3,5-Me3C6H3; (f) 1,2,3-Me3C6H3. Treatment of 2 with xylyl isocyanide (XylNC) in the presence of NaPF6 produced the F-coordinated complex [(η6-arene)RuCl]2(μ-dpmf)(PF6)2 3a without containing XylNC. Reactions of 1 with 1,1′-bis(diphenylphosphino)ferrocene (dppf) formed the bridged complexes [(arene)RuCl2]2(μ-dppf)] 4, as well as the dpmf complexes. The similar reactions in the presence of NaPF6 gave the chelated complexes [(η6-arene)RuCl(dppf-P,P′)](PF6) 5. Crystal structures of 2a, 2d·2CH2Cl2, 4a·CH2Cl2 and 5b were confirmed by X-ray analyses and they have three-legged piano-stool structures. Crystal data are as follows: 2a triclinic, space group P1, with a=12.802(6), b=19.111(6), c=11.438(4) A, α=98.93(3), β=108.57(3), γ=90.42(3)°, V=2615(1) A3, Z=2 [R=0.051, Rw=0.052 for 4114 independent reflections with I>3.0σ(I)]; 2d·2CH2Cl2 monoclinic, space group C2/c, a=38.379(6), b=9.903(3), c=17.381(4) A, β=113.91(1)°, V=6038 A3 and Z=4 [R=0.057, Rw=0.054 for 1882 independent reflections with I>3.0σ(I)]; 4a·CH2Cl2 triclinic P1, with a=15.044(7), b=17.664(3), c=10.586(2) A, α=99.64(2), β=95.85(2), γ=94.74(2)°, V=2744(1) A3, Z=2 [R=0.065, Rw=0.072 for 4301 independent reflections I>3.0σ(I)]; 5b monoclinic, space group P21/n, a=15.036(4), b=17.192(5), c=15.983(3) A, β=92.92(2)°, V=4126(1) A3, Z=4 [R=0.070, Rw=0.079 for 3389 independent reflections I>3σ(I)]. Conformation of the ferrocenyl skeletons were determined by dihedral angles containing two Cp rings. In cyclic voltammertry (CV) of these complexes the Fe(II)/Fe(III) redox couples were quasi-reversible, but the Ru moieties were irreversible.