Formation of ruthenium thiolates via complexes of molecular hydrogen

Journal Article · Wed Apr 27 00:00:00 EDT 1994 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00087a043· OSTI ID:6835737

Field, L D; Hambley, T W; Yau, B C.K. ^[1]

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1. Univ. of Sydney, Sydney (Australia)

RuH[sub 2](DMPE)[sub 2][DMPE = 1,2-bis(dimethylphosphino)ethane] was synthesized by reduction of trans-RuCl[sub 2](DMPE)[sub 2] with sodium/2-propanol. Protonation of RuH[sub 2](DMPE)[sub 2] with weak organic acids such as methanol, ethanol, and thiols affords the molecular hydrogen complex trans-[RuH([eta][sup 2]-H[sub 2])(DMPE)[sub 2]][sup +], which has an [eta][sup 2]-bound H[sub 2] ligand and a [sigma]-bound hydride ligand. T[sub 1] measurements and the observation of a large [sup 1]J[sub HD] coupling in the [eta][sup 2]-HD isotopomer ligand support the [open quotes]nonclassical[close quotes] structure. In the [sup 1]H NMR spectrum of the trans-[RuH([eta][sup 2]-HD)(DMPE)[sub 2]][sup +] isotopomer, the proton-proton coupling (across the metal center) between [sigma]-H and [sup 1]H in the [eta][sup 2]-HD was measured at 4.5 Hz. Between 220 and 300 K, the molecular hydrogen complex undergoes intermolecular exchange with the protonating reagent and all the ruthenium-bound hydrogens in the molecular hydrogen complex undergo intramolecular exchange. The weakly bound [eta][sup 2[minus]]H[sub 2] ligand is readily displaced by alkane- and arenethiols to give trans-monothiolate hydrides. With thiophenol, a second substitution occurs to give a dithiolate complex. Crystals of trans-Ru(SPH)[sub 2](DMPE)[sub 2] are; monoclinic, space group P2[sub 1]/a, with a - 15.035(3) [angstrom], b = 9.881(3) [angstrom], c = 19.604(4) [angstrom], [beta] = 97.51(2)[degrees], Z = 4, and R = 0.029 [3348 reflections used with I>2.5[sigma](I)]. The structural analysis shows that Ru is coordinated by two bidentate phosphine and two monodentate benzenethiolate ligands in a trans arrangement.

• OSTI ID: 6835737
• Journal Information: Inorganic Chemistry; (United States), Vol. 33:9; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
HYDROGEN COMPLEXES
CHEMICAL REACTIONS
RUTHENIUM COMPLEXES
CHEMICAL PREPARATION
LATTICE PARAMETERS
MONOCLINIC LATTICES
NUCLEAR MAGNETIC RESONANCE
STRUCTURAL CHEMICAL ANALYSIS
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
MAGNETIC RESONANCE
RESONANCE
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties