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

Journal Article · Wed Dec 23 00:00:00 EST 1992 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00052a029· OSTI ID:6725463

Hampton, C R.S.M.; Butler, I R; Cullen, W R; James, B R ^[1]; Charland, J P ^[2]; Simpson, J ^[3]

---

1. Univ. of British Columbia, Vancouver (Canada)
2. National Research Council, Ottawa, Ontario (Canada)
3. Univ. of Otago, Dunedin (New Zealand)

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.

• OSTI ID: 6725463
• Journal Information: Inorganic Chemistry; (United States), Vol. 31:26; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CHELATES
CRYSTAL STRUCTURE
HYDROGEN COMPOUNDS
IRON COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RUTHENIUM CHLORIDES
RUTHENIUM HYDRIDES
ACTIVATION ENERGY
LATTICE PARAMETERS
LIGANDS
NUCLEAR MAGNETIC RESONANCE
ORTHORHOMBIC LATTICES
PHOSPHINES
X-RAY DIFFRACTION
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
DIFFRACTION
ENERGY
HALIDES
HALOGEN COMPOUNDS
HYDRIDES
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
PHOSPHORUS COMPOUNDS
REFRACTORY METAL COMPOUNDS
RESONANCE
RUTHENIUM COMPOUNDS
SCATTERING
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties