Classical and nonclassical polyhydride ruthenium(II) complexes stabilized by the tetraphosphine P(CH sub 2 CH sub 2 PPh sub 2 ) sub 3

Journal Article · Wed Jan 23 04:00:00 EST 1991 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00002a024· OSTI ID:5937125

Bianchini, C; Perez, P J; Peruzzini, M; Zanobini, F; Vacca, A ^[1]

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1. Istituto per lo Studio della Stereochimica ed Energetica dei Composti di Coordinazione del CNR, Firenze (Italy)

The dichloride ((PP{sub 3})RuCl{sub 2}) (1) is selectively transformed into ((PP{sub 3})Ru(H)({eta}{sup 1}-BH{sub 4})) (2), ((PP{sub 3})Ru(H)Cl) (3), and ((PP{sub 3})Ru(H){sub 2}) (4) by reaction with NaBH{sub 4}, LiHBEt{sub 3}, and LiAlH{sub 4}, respectively (PP{sub 3} = P(CH{sub 2}CH{sub 2}PPh{sub 2}){sub 3}). Complex 2 is fluxional on the NMR time scale in ambient-temperature solutions due to equilibration of the BH{sub 4}{sup {minus}} hydrogens through cleavage of the Ru-H{sub b}-B bridge and interconversion of H{sub t} by rotation. The hydride-tetrahydroborate complex exhibits amphoteric nature: it reacts with protic acids, yielding the cis-hydride dihydrogen complex ((PP{sub 3})Ru(H)({eta}{sup 2}-H{sub 2}))Y (Y = PF{sub 6}, 6a; BPh{sub 4}, 6b), and with bases such as PEt{sub 3} or KO{sup t}Bu, converting to the dihydride 4. The latter compound can be obtained also by thermal decomposition of 2 in refluxing toluene or benzene. Complexes 6a,b can be prepared by reaction of the dihydride 4 with protic acids. In the solid state and in solution at low temperature ((PP{sub 3})Ru(H)({eta}{sup 2}-H{sub 2})){sup +} is octahedral, and the hydride and dihydrogen ligands occupy mutually cis positions. At ambient temperature in solution the complex is trigonal-bipyramidal and the equilibration of the hydrogens might proceed through an H{sub 3} unit occupying an axial position trans to the bridgehead phosphorus atom of PP{sub 3}. 36 refs., 6 figs., 2 tabs.

• OSTI ID: 5937125
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 30:2; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

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ALKENES
ALKYNES
AROMATICS
CATALYSIS
CATALYTIC EFFECTS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COMPLEXES
DATA
EXPERIMENTAL DATA
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGENATION
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
RUTHENIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES