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Title: 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

Abstract

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 = Osmore » (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.« less

Authors:
; ; ; ; ;  [1];  [2];  [3]
  1. Universidad de Zaragoza (Spain)
  2. Universidad de Zaragoza (Spain) Universitaet Wuerzburg (Germany)
  3. Universitaet Wuerzburg (Germany)
Publication Date:
OSTI Identifier:
6708823
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (United States)
Additional Journal Information:
Journal Volume: 31:26; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
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

Citation Formats

Esteruelas, M A, Garcia, M P, Lopez, A M, Oro, L A, Ruiz, N, Valero, C, Schluenken, C, and Werner, H. 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. United States: N. p., 1992. Web. doi:10.1021/ic00052a038.
Esteruelas, M A, Garcia, M P, Lopez, A M, Oro, L A, Ruiz, N, Valero, C, Schluenken, C, & Werner, H. 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. United States. doi:10.1021/ic00052a038.
Esteruelas, M A, Garcia, M P, Lopez, A M, Oro, L A, Ruiz, N, Valero, C, Schluenken, C, and Werner, H. Wed . "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". United States. doi:10.1021/ic00052a038.
@article{osti_6708823,
title = {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},
author = {Esteruelas, M A and Garcia, M P and Lopez, A M and Oro, L A and Ruiz, N and Valero, C and Schluenken, C and Werner, H},
abstractNote = {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.},
doi = {10.1021/ic00052a038},
journal = {Inorganic Chemistry; (United States)},
issn = {0020-1669},
number = ,
volume = 31:26,
place = {United States},
year = {1992},
month = {12}
}