Reactivity of MH([eta][sup 2]-H[sub 2]BH[sub 2])(CO)(PiPr[sub 3])[sub 2] (M = Os, Ru) toward electrophiles: Synthesis of new hydridocarbonylosmium(II) and -ruthenium(II) complexes containing triisopropylphosphine as ligand

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

DOI:https://doi.org/10.1021/ic00052a038· OSTI ID:6708823

Esteruelas, M A; Garcia, M P; Lopez, A M; Oro, L A; Ruiz, N; Valero, C ^[1]; Schluenken, C ^[2]; Werner, H ^[3]

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1. Universidad de Zaragoza (Spain)
2. Universidad de Zaragoza (Spain) Universitaet Wuerzburg (Germany)
3. Universitaet Wuerzburg (Germany)

The complexes [(PiPr[sub 3])[sub 2](CO)HM([mu],[eta][sup 4]-BH[sub 4])MH(CO)(PiPr[sub 3])[sub 2]]BF[sub 4] (5, 6), MH([eta][sup 2]-O[sub 2]CR[sup *])(CO)(PiPr[sub 3])[sub 2] (7-13) and MH(pz)(CO)(Hpz)(PiPr[sub 3])[sub 2] (14, 15) (M = Os, Ru) have been prepared by reaction of MH([eta][sup 2]-H[sub 2]BH[sub 2])(CO)(PiPr[sub 3])[sub 2] (M = Os, Ru) with HBF[sub 4], R[sup *]CO[sub 2]H (R[sup *] = (S)-CH(NaphOMe)Me, (R)-CH(OMe)Ph, (R)-C(CF[sub 3])(OMe)Ph, (S)-[ovr CHOC([double bond]O)CH[sub 2]C]H[sub 2]) and Hpz (pyrazole), respectively. 5 and 6 react with molecular hydrogen, tetrafluorobenzobarrelene (TFB), methyl vinyl ketone, acetonitrile, and acetone to give [OsH([eta][sup 2]-H[sub 2])(CO)(PiPr[sub 3])[sub 2]][sup +] (16), [OsH([eta][sup 2]-H[sub 2])(CO)(OH[sub 2])(PiPr[sub 3])[sub 2]][sup +] (17), [OsH(CO)(TFB)(PiPr[sub 3])[sub 2]][sup +] (18), [[ovr OsH(CO)([pi]-CH[sub 2][double bond]CHC([double bond]O])CH[sub 3])(PiPr[sub 3])[sub 2]][sup +] (19), [MH(CO)(CH[sub 3]CN)[sub 2](PiPr[sub 3])[sub 2]][sup +] (M = Os (20), Ru (21)) and [RuH(CO)([eta][sup 1]-(CH[sub 3])[sub 2]CO)[sub 2](PiPr[sub 3])[sub 2]][sup +] (22). In solution 22 dissociates an acetone molecule to give [RuH(CO)([eta][sup 1]-(CH[sub 3])[sub 2]CO)(PiPr[sub 3])[sub 2]][sup +] (23). The cations [MH(CO)(Hpz)[sub 2](PiPr[sub 3])[sub 2]][sup +] (M = Os (24), Ru (25)) were obtained by addition of HBF[sub 4] to diethyl ether solutions of 14 and 15. The latter react with HCl to give a mixture of two isomers of MHCl(CO)(Hpz)(PiPr[sub 3])[sub 2] (M = Os (26), Ru (27)). The catalytic activity of 7-13 in asymmetric hydrogen transfer from 2-propanol to acetophenone is also described. The osmium carboxylates lead to considerably higher optical yields than ruthenium complexes. 31 refs., 5 figs.

• OSTI ID: 6708823
• 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
CARBONYLS
CHEMICAL PREPARATION
HYDROGEN TRANSFER
HOMOGENEOUS CATALYSIS
OSMIUM COMPOUNDS
RUTHENIUM HYDRIDES
CHEMICAL REACTIONS
NUCLEAR MAGNETIC RESONANCE
PHOSPHINES
PYRAZOLES
AZOLES
CATALYSIS
HETEROCYCLIC COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOSPHORUS COMPOUNDS
REFRACTORY METAL COMPOUNDS
RESONANCE
RUTHENIUM COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties