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UBC Theses and Dissertations

Activation of dihydrogen by ruthenium complexes containing chelating phosphines Joshi, Ajey Madhav


The previously reported synthesis of dinuclear mixed-valence ruthenium complexes of general formula Ru₂Cl₅(P-P)₂, P-P = DPPP, DPPB, 5,5-CHIRAPHOS, or R.R-DIOP, has been extended to include other diphosphines: P-P = DPPN, DPPH, rac-DPPCP, rac-DPCYCP, S,S-BDPP, R- and S-BINAP, or S-PHENOP. The complexes are prepared by the reaction of RuCl₃P₂(DMA)-DMA, P = PPh₃ or P(p-tolyl)₃, with one equivalent of the appropriate diphosphine. The H₂-reduction of Ru₂Cl₅(P-P)₂ complexes in DMA, or in toluene in the presence of an added base, affords the corresponding dimeric Ru(II) complexes [RuCl(P-P)(µ-Cl)]₂, P-P = DPPN, R- or S-BINAP, or S,S-BDPP, which have been characterised by NMR spectroscopy. The [RuCl(P-P)(µ,-Cl)]₂ complexes (Structure I) show a great propensity to form trichloro-bridged dinuclear species (Structure II) in the presence of neutral coordinating ligands (L). A series of trichloro-bridged complexes of the type [(L)(P-P)Ru-(µ-Cl)₃RuCl(P-P)] (e.g. P-P = DPPB; L = NEt₃, NHBu₂, CO, DMA, PhCN, Mel) have been isolated or studied in situ and characterised spectroscopically. The molecular structure of the DMSO analogue shows an S-bonded DMSO ligand with an unsymmetrical arrangement of the chelating DPPB ligand (cf. Structure II). [ Formulas omitted ] The reaction of [RuCl(DPPB)(µ,-Cl)]₂ with H₂ has been investigated. In benzene or toluene, in the absence of an added base, dihydrogen adds reversibly to the ruthenium dimer to give the remarkably simple molecular hydrogen complex (L = η²-H₂; Structure II); the η²-H₂ ligand (with an H-H distance of 0.86 Å as estimated by ¹H NMR variable temperature spin-lattice relaxation data; T₁(min) - 12 ms at 300 MHz) is replaceable by N2. The reaction of [RuCl(P-P)(µ-Cl)]₂, P-P = DPPB or 5,5-CHIRAPHOS, with H₂ in the presence of NEt₃ as the added base yields the corresponding trinuclear Ru(II) hydride complex, [RuHCl(P-P)]₃, along with [(NEt₃)(P-P)Ru(u-Cl)3RuCl(P-P)]. The hydride complexes had been synthesised previously, albeit in low yields (<10%), and the crystal structure of the CHIRAPHOS derivative obtained. During the present work the original synthetic procedure has been modified to obtain the desired [RuHCl(P-P)]₃ complexes in ∼50% yield. In addition, these species have been characterised completely by NMR spectroscopy. The conversion of [RuCl(P-P)-((µ-Cl)]₂ to the corresponding hydride derivative likely proceeds via deprotonation by NEt₃ of the initially formed molecular hydrogen species. Under hydrogen atmosphere, [RuHClQDPPB)]₃ breaks down to form the dinuclear derivative [(η²-H₂)(DPPB)Ru(µ-H)(µ-Cl)₂RuH(DPPB)] containing a molecular hydrogen ligand, which has been identified by ¹H NMR T₁ measurements; similar complexes, but with a nitrile ligand (MeCN or PhCN) in place of the η²-H₂, have also been observed. Alternative routes to ruthenium complexes containing only one diphosphine per Ru ("RuII(P-P)") have been investigated. Some of the trichloro-bridged derivatives (e.g. L = amine, CO; Structure II, see above) are also accessible through reactions of the mixed-phosphine complex RuCl₂(DPPB)(PPh₃) with amines and aldehydes, respectively. Studies on the reactions of RuCl₂(DMSO)₄ or [RuCl(p-cymene)-(µ,-Cl)]₂ with one equivalent of diphosphines show that the nature and the distribution of product(s) (i.e. RuCl₂(P-P)₂ vs. "RuCl₂(P-P)") are greatly influenced by the chelate size of the diphosphine. The "RuCl₂(P-P)" species is observed only for those phosphines which form at least a six-membered ring upon coordination to the metal. Solid-state ³¹P NMR studies indicate that the structure of RuCl₂(DPPB)(PPh₃) is similar to that of RuCl₂(PPh₃)₃, which has been characterised previously by X-ray crystallography. Reactions of RuCl₂(DPPB)(PPh₃) with chelating ligands afford six-coordinate complexes of the type RuCl₂(DPPB)(L-L), L-L = PPh₂Py, DPPM, or norbornadiene; the corresponding hydridochloro derivatives are obtained when the reactions are conducted under an atmosphere of H₂ in the presence of Proton Sponge®. The dimeric [RuCl(P-P)(µ-Cl)]₂ and the trinuclear [RuHCl(P-P)]₃ complexes described in this study are effective catalyst precursors for the hydrogenation of various alkene, ketone, imine, and nitrile substrates under relatively mild conditions (30-100 °C, 1-12 atm of H₂). A detailed kinetic study on the hydrogenation of styrene catalysed by [RuCl(DPPB)(µ-Cl)]₂ shows a first-order dependence of the maximum rate on catalyst concentration, a first- to zero-order dependence on styrene concentration and a zero- to first-order dependence on the H₂ pressure. A mechanism involving formation of the molecular hydrogen (η²-H₂) complex (see above) followed by hydrogen transfer to the substrate is proposed to account for the observations, and the rate constants at 30 ºC for the various steps have been determined. Preliminary data on acetophenone and benzonitrile hydrogenation shows that the trinuclear hydride complexes are an order of magnitude more effective than the corresponding dimeric precursors.

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