Molecular dihydrogen and hydrido derivatives of ruthenium(II) complexes containing chelating ferrocenyl-based tertiary phosphine amine ligands and/or monodentate tertiary phosphine ligands

• Published in: Inorganic chemistry 1992-12, Vol.31 (26), p.5509-5520
• Main Authors: Hampton, Cashman R. S. M, Butler, Ian R, Cullen, William R, James, Brian R, Charland, Jean Pierre, Simpson, J
• Format: Article
• Language: English
• Subjects: ACTIVATION ENERGY; CHELATES; Chemistry; CHLORIDES; CHLORINE COMPOUNDS; COHERENT SCATTERING; COMPLEXES; Condensed matter: structure, mechanical and thermal properties; Coordination compounds; CRYSTAL LATTICES; CRYSTAL STRUCTURE; DIFFRACTION; ENERGY; Exact sciences and technology; HALIDES; HALOGEN COMPOUNDS; HYDRIDES; HYDROGEN COMPOUNDS; Inorganic chemistry and origins of life; Inorganic compounds; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; IRON COMPOUNDS; LATTICE PARAMETERS; LIGANDS; MAGNETIC RESONANCE; Metal complexes; NUCLEAR MAGNETIC RESONANCE; ORGANIC COMPOUNDS; ORGANOMETALLIC COMPOUNDS; ORTHORHOMBIC LATTICES; PHOSPHINES; PHOSPHORUS COMPOUNDS; Physics; Preparations and properties; REFRACTORY METAL COMPOUNDS; RESONANCE; RUTHENIUM CHLORIDES; RUTHENIUM COMPOUNDS; RUTHENIUM HYDRIDES; SCATTERING; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; TRANSITION ELEMENT COMPOUNDS 400201 > Chemical & Physicochemical Properties; X-RAY DIFFRACTION
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic00052a029

Reactions of complexes of the type RuCl[sub 2](PPh[sub 3])(P-N) with H[sub 2] are reported, where P-N represents the chelating ferrocene-based ligands ([eta]-C[sub 5]H[sub 5])Fe([eta]-C[sub 5]H[sub 3](CHMeNMe[sub 2])PR[sub 2]-1,2) with R = i-Pr (the isoPFA ligand) or Ph (the PPFA ligand). Depending on the solvent(s) used, and absence or presence of added base, RuCl[sub 2](PPh[sub 3])(isoPFA) (2b) generates the dinuclear [eta][sup 2]-H[sub 2] complexes L[sub 2]([eta][sup 2]-H[sub 2])Ru([mu]-Cl)[sub 2]([mu]-H)Ru(H)(PPh[sub 3])[sub 2] where L[sub 2] = isoPFA (complex 3) or L[sub 2] = (PPh[sub 3])[sub 2] (complex 4). n-Butanol solutions of RuCl[sub 2](PPh[sub 3])(PPFA) (2a) under H[sub 2] also yield 4, as well as Ru(H)Cl[sub 2](PPh[sub 3])(PPFA[center dot]H)(BuOH), a zwitterionic species containing a protonated amine moiety stabilized by coordinated n-BuOH, which is likely intermediate in heterolytic cleavage of the H[sub 2]: the complex RuH(Cl)(PPh[sub 3])(isoPFA) (5), together with a hybrido carbonyl species, is isolated from methanol solutions of 2b. Complexes 2b, 3, 4, and 5 are characterized by X-ray crystallography; the mononuclear complexes 2b and 5 are orthorhombic with space groups F2dd and P2[sub 1]2[sub 1]2[sub 1], respectively. Variable-temperature [sup 1]H- and [sup 31]P-NMR data for 3 reveal fast exchange between the [eta][sup 2]-H[sub 2] and the [mu]-H at 20[degrees]C and a slower exchange of this system with the terminal hydride; corresponding data for 4 and its P(p-tolyl)[sub 3] analogue 7 show a faster exchange involving all the hydrogens. Activation parameters are determined for the exchange processes. 48 refs., 13 figs., 7 tabs.