25087-65-4

Upstream product

• 1333-74-0 hydrogen 
• 143-66-8 sodium tetraphenyl borate 
• 356528-26-2 Ru((C₆H₅)2PCH₂CH₂P(C₆H₅)2)2H(FHF) 
• 75-09-2 dichloromethane 
• 67-66-3 chloroform 
• 75-36-5 acetyl chloride 
• 108-90-7 chlorobenzene 
• 98-88-4 benzoyl chloride 
• 67-56-1 methanol 
• 7647-01-0 hydrogenchloride 
• 67969-82-8 tetrafluoroboric acid diethyl ether 
• 151840-73-2 [(1,2-bis(diphenylphosphino)ethane)2RuCl]BF₄ 
• 311819-28-0 RuH(OAc)(PPh₃)3 

Relevant academic research and scientific papers

A convenient route for the preparation of the monohydride catalyst trans-[RuCl(H)(dppe)2] (dppe = Ph2PCH2CH 2PPh2): Improved synthesis and crystal structure

A novel and improved room temperature synthesis of the monohydride catalyst trans-[RuCl(H)(dppe)2] complex (1, dppe (1,2-bis(diphenylphosphino) ethane) = Ph2PCH2CH2PPh2) proceeds through oxidation of methanol (the solvent) by the pentacoordinated cis-[RuCl(dppe)2][PF6] complex and t-BuOK as the base is described. Compound 1 was fully characterized by NMR (1H, 13C, 31P), ESI-MS(TOF +), FTIR and elemental analysis. The X-ray structure of 1 was reported for the first time and unambiguously confirms the trans-configuration of the complex.

B-H bond activation using an electrophilic metal complex: Insights into the reaction pathway

A highly electrophilic ruthenium center in the [RuCl(dppe) 2][OTf] complex brings about the activation of the B-H bond in ammonia borane (H3N·BH3, AB) and dimethylamine borane (Me2HN·BH3, DMAB). At room temperature, the reaction between [RuCl(dppe)2][OTf] and AB or DMAB results in trans-[RuH(η2-H2)(dppe)2][OTf], trans-[RuCl(η2-H2)(dppe)2][OTf], and trans-[RuH(Cl)(dppe)2], as noted in the NMR spectra. Mixing the ruthenium complex and AB or DMAB at low temperature (198/193 K) followed by NMR spectral measurements as the reaction mixture was warmed up to room temperature allowed the observation of various species formed enroute to the final products that were obtained at room temperature. On the basis of the variable-temperature multinuclear NMR spectroscopic studies of these two reactions, the mechanistic insights for B-H bond activation were obtained. In both cases, the reaction proceeds via an η1-B-H moiety bound to the metal center. The detailed mechanistic pathways of these two reactions as studied by NMR spectroscopy are described.

Making the true "CP" ligand

Cyaphide attained: A high-yielding synthesis for the first stable terminal cyaphide complex [RuH(CP)(dppe)2] (dppe = bis(1,2- diphenylphosphinoethane); see structure: P orange, Ru silver, C gray, H white) was developed from the silyl-substitute

Synthesis, characterisation and reactivity of ruthenium bis-bifluoride, ruthenium hydride bifluoride and ruthenium hydride fluoride complexes

Bifluoride complexes, trans-[Ru(depe)2H(FHF)] (1), trans-[Ru(dppe)2H(FHF)] (2), trans-[Ru(dppp)2H(FHF)] (3) and cis-[Ru(PMe3)4(FHF)2] (4) (depe = Et2PCH2CH2PEt2, dppe = Ph2PCH2CH2PPh2, dppp = Ph2PCH2CH2CH2PPh2) were synthesised from the reactions of the corresponding cis-dihydride complexes with NEt3·3HF in THF. The characteristic features of the low temperature NMR spectra of the bifluoride complexes include 19F resonances at ca. δ -300 for the proximal fluorine and ca. δ -165 for the distal fluorine. The acidic protons resonate at ca. δ 13. The value of J(HF) for the distal fluorine lies in the range 300-400 Hz. The bifluoride ligands exhibit characteristic vibrations at ca. 2300 cm-1 and ca. 2430 cm-1 in the IR spectrum. All the complexes exhibit dynamic exchange processes, probably due to dissociation of FHF-. In addition, complex 3 undergoes a ring flipping process that is suppressed at low temperature. The X-ray crystal structure of 3 has been obtained. The bifluoride ligand is disordered over two positions about the inversion centre. The Ru-F distance is 2.351(5) A and the F···F distance is 2.290(8) A, the Ru-F···F angle is 149.7°. The X-ray crystal structure for 4 reveals that the Ru-F distances are 2.149(5) A and 2.150(4) A, the F···F bond lengths are 2.323(8) A and 2.329(8) A, with Ru-F···F angles of 128.5(3)° and 138.4(3)°. The two bifluoride ligands are cis to each other. Reaction of 1 and 3 with [NMe4]F yields trans-[Ru(depe)2(H)F] 5 and trans-[Ru(dppp)2(H)F] 6. Reaction of 2 with Me3SiX (X = N3, OTf) yields trans-[Ru(dppe)2(H)N3] and [Ru(dppe)2(H)]OTf. Reactions with several halo-organic compounds yields trans-[Ru(dppe)2(H)X] (X = Cl, Br and I). The organic products from CH3I, CH3COCl and C6H5COCl were identified as CH3F, CH3COF and C6H5COF respectively.

Formation of ammonia in the reactions of a tungsten dinitrogen with ruthenium dihydrogen complexes under mild reaction conditions

Treatment of cis-[W(N2)2(PMe2Ph)4] (5) with an equilibrium mixture of trans-[RuCl(η2-H2)(dppp)2]X (3) with pKa = 4.4 and [RuCl(dppp)2]X (4) [X = PF6, BF4, or OTf; dppp = 1,3-bis(diphenylphosphino)propane] containing 10 equiv of the Ru atom based on tungsten in benzene-dichloroethane at 55°C for 24 h under 1 atm of H2 gave NH3 in 45-55% total yields based on tungsten, together with the formation of trans-[RuHCl(dppp)2] (6). Free NH3 in 9-16% yields was observed in the reaction mixture, and further NH3 in 36-45% yields was released after base distillation. Detailed studies on the reaction of 5 with numerous Ru(η2-H2) complexes showed that the yield of NH3 produced critically depended upon the pKa value of the employed Ru(η2-H2) complexes. When 5 was treated with 10 equiv of trans-[RuCl(η2-H2)(dppe)2]X (8) with pKa = 6.0 [X = PF6, BF4, or OTf; dppe = 1,2-bis(diphenylphosphino)ethane] under 1 atm of H2, NH3 was formed in higher yields (up to 79% total yield) compared with the reaction with an equilibrium mixture of 3 and 4. If the pKa value of a Ru(η2-H2) complex was increased up to about 10, the yield of NH3 was remarkably decreased. In these reactions, heterolyfic cleavage of H2 seems to occur at the Ru center via nucleophilic attack of the coordinated N2 on the coordinated H2 where a proton (H+) is used for the protonation of the coordinated N2 and a hydride (H-) remains at the Ru atom. Treatment of 5, trans-[W(N2)2(PMePh2)4] (14), or trans-[M(N2)2(dppe)2] [M = Mo (1), W (2)] with Ru(η2-H2)complexes at room temperature led to isolation of intermediate hydrazido(2-) complexes such as trans-[W(OTf)(NNH2)(PMe2Ph)4]OTf (19), trans-[W(OTf)(NNH2)(PMePh2)4]OTf (20), and trans-[WX(NNH2)(dppe)2]+ [X = O[Tf (15), F (16)]. The molecular structure of 19 was determined by X-ray analysis. Further ruthenium-assisted protonation of . hydrazido(2-) intermediates such as 19 with H2 at 55 °C was considered to result in the formation of NH3, concurrent with the generation of W(VI)species. All of the electrons required for the reduction of N2 are provided by the zerovalent tungsten.

Mechanisms of reactions of dihydrogen complexes: Formation of trans-[RuH(H2)(dppe)2]+ and substitution of coordinated dihydrogen

The reactions between cis-[RuH2(DPPE)2] and a number of acids in THF solution (DPPE = Ph2PCH2CH2PPh2) show biphasic kinetics, with initial formation of trans-[RuH(H2)(DPPE)2]+ followed by slower substitution of coordinated dihydrogen by the anion of the acid. The formation of the dihydrogen complex is a second-order process that occurs with an inverse kinetic isotope effect and rate constants kHX strongly dependent on the nature of the acid. There is a linear correlation between the values of log kHX for cis-[RuH2(DPPE)2] and the related cis-[FeH2(PP3)] [PP3 = P(CH2CH2PPh2)3] that leads to two parameters, S and R, that can be used as a measure of the selectivity and intrinsic reactivity of the dihydride toward acids. The possible contributions to the values of these parameters are discussed, especially the role of the isomerization of the starting complex and the basicity of the reacting species. The substitution of coordinated dihydrogen in trans-[RuH(H2)(DPPE)2]+ occurs through a simple dissociative mechanism instead of the more complicated one previously proposed for substitutions in the analogous Fe complex; the mechanistic change is associated with the relative strength of the M-H2 and M-P(chelate) bonds.

Synthesis and reactivity of (DPPE){(C6H5)(C6H4)PCH 2CH2P(C6H5M)2}RuCl

The compound trans-(DPPE)2RuCl2 (1) undergoes reaction in neat trimethylaluminum to afford two products: trans-(DPPE)2RuCH3Cl (2) and (DPPE)-{(C6H5)(C6H4)PCH 2/s

PHOSPHINE SUBSTITUTION AND PHOSPHINE INDUCED REDUCTIVE ELIMINATION REACTIONS: SYNTHESIS OF ZEROVALENT RUTHENIUM FLUOROPHOSPHINE COMPLEXES FROM HYDRIDO(ACETATO)TRIS(TRIPHENYLPHOSPHINE)RUTHENIUM(II)

Substitution of PPh3 from the bidentate acetatohydridoruthenium(II) complex RuH(CH3OCO)(PPh3)3 with various ligands, L, leads to unidentate acetatohydrido compounds with replacement of one, two or all PPh3 ligands depending on L (L = t=BuNC, PF2NMe2, P(OC