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Title: Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol

Abstract

A ruthenium hydride with a bulky tetra-substituted Cp ligand, (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H (Cp{sup iPr{sub 4}} = C{sub 5}(i-C{sub 3}H{sub 7}){sub 4}H) was prepared from the reaction of Ru{sub 3}(CO){sub 12} with 1,2,3,4-tetraisopropylcyclopentadiene. The molecular structure of (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H was determined by X-ray crystallography. The ruthenium hydride complex (C{sub 5}Bz{sub 5})Ru(CO){sub 2}H (Bz = CH{sub 2}Ph) was similarly prepared. The Ru-Ru bonded dimer, [(1,2,3-trimethylindenyl)Ru(CO){sub 2}]{sub 2}, was produced from the reaction of 1,2,3-trimethylindene with Ru{sub 3}(CO){sub 12}, and protonation of this dimer with HOTf gives {l_brace}[(1,2,3-trimethylindenyl)Ru(CO){sub 2}]{sub 2}-({mu}-H){r_brace}{sup +}OTf{sup -}. A series of ruthenium hydride complexes CpRu(CO)(L)H [L = P(OPh){sub 3}, PCy{sub 3}, PMe{sub 3}, P(p-C{sub 6}H{sub 4}F){sub 3}] were prepared by reaction of Cp(CO){sub 2}RuH with added L. Protonation of (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H, Cp*Ru(CO){sub 2}H, or CpRu(CO)[P-(OPh){sub 3}]H by HOTf at -80 C led to equilibria with the cationic dihydrogen complexes, but H{sub 2} was released at higher temperatures. Protonation of CpRu[P(OPh){sub 3}]{sub 2}H with HOTf gave an observable dihydrogen complex, {l_brace}CpRu[P-(OPh){sub 3}]{sub 2}({eta}{sup 2}-H{sub 2}){r_brace}+OTf{sup -} that was converted at -20 C to the dihydride complex {l_brace}CpRu[P(OPh){sub 3}]{sub 2}(H){sub 2}{r_brace}{sup +}OTf{sup -}. These Ru complexes serve as catalyst precursors for the catalytic deoxygenation of 1,2-propanediolmore » to give n-propanol. The catalytic reactions were carried out in sulfolane solvent with added HOTf under H{sub 2} (750 psi) at 110 C.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
BROOKHAVEN NATIONAL LABORATORY (BNL)
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
979361
Report Number(s):
BNL-90105-2009-JA
Journal ID: ISSN 0020-1669; INOCAJ; R&D Project: CO-004; KC0201010; TRN: US1003358
DOE Contract Number:
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 48; Journal Issue: 14
Country of Publication:
United States
Language:
English
Subject:
43 PARTICLE ACCELERATORS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCELERATORS; CARBONYLS; CATALYSTS; CRYSTALLOGRAPHY; DIMERS; MOLECULAR STRUCTURE; PHOSPHINES; RUTHENIUM; RUTHENIUM HYDRIDES; SOLVENTS; SYNTHESIS

Citation Formats

Bullock, R.M., Ghosh, P., Fagan, P.J., Marshall, W.J., and Hauptman, E. Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol. United States: N. p., 2009. Web.
Bullock, R.M., Ghosh, P., Fagan, P.J., Marshall, W.J., & Hauptman, E. Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol. United States.
Bullock, R.M., Ghosh, P., Fagan, P.J., Marshall, W.J., and Hauptman, E. 2009. "Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol". United States. doi:.
@article{osti_979361,
title = {Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol},
author = {Bullock, R.M. and Ghosh, P. and Fagan, P.J. and Marshall, W.J. and Hauptman, E.},
abstractNote = {A ruthenium hydride with a bulky tetra-substituted Cp ligand, (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H (Cp{sup iPr{sub 4}} = C{sub 5}(i-C{sub 3}H{sub 7}){sub 4}H) was prepared from the reaction of Ru{sub 3}(CO){sub 12} with 1,2,3,4-tetraisopropylcyclopentadiene. The molecular structure of (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H was determined by X-ray crystallography. The ruthenium hydride complex (C{sub 5}Bz{sub 5})Ru(CO){sub 2}H (Bz = CH{sub 2}Ph) was similarly prepared. The Ru-Ru bonded dimer, [(1,2,3-trimethylindenyl)Ru(CO){sub 2}]{sub 2}, was produced from the reaction of 1,2,3-trimethylindene with Ru{sub 3}(CO){sub 12}, and protonation of this dimer with HOTf gives {l_brace}[(1,2,3-trimethylindenyl)Ru(CO){sub 2}]{sub 2}-({mu}-H){r_brace}{sup +}OTf{sup -}. A series of ruthenium hydride complexes CpRu(CO)(L)H [L = P(OPh){sub 3}, PCy{sub 3}, PMe{sub 3}, P(p-C{sub 6}H{sub 4}F){sub 3}] were prepared by reaction of Cp(CO){sub 2}RuH with added L. Protonation of (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H, Cp*Ru(CO){sub 2}H, or CpRu(CO)[P-(OPh){sub 3}]H by HOTf at -80 C led to equilibria with the cationic dihydrogen complexes, but H{sub 2} was released at higher temperatures. Protonation of CpRu[P(OPh){sub 3}]{sub 2}H with HOTf gave an observable dihydrogen complex, {l_brace}CpRu[P-(OPh){sub 3}]{sub 2}({eta}{sup 2}-H{sub 2}){r_brace}+OTf{sup -} that was converted at -20 C to the dihydride complex {l_brace}CpRu[P(OPh){sub 3}]{sub 2}(H){sub 2}{r_brace}{sup +}OTf{sup -}. These Ru complexes serve as catalyst precursors for the catalytic deoxygenation of 1,2-propanediol to give n-propanol. The catalytic reactions were carried out in sulfolane solvent with added HOTf under H{sub 2} (750 psi) at 110 C.},
doi = {},
journal = {Inorganic Chemistry},
number = 14,
volume = 48,
place = {United States},
year = 2009,
month = 7
}
  • A ruthenium hydride with a bulky substituted Cp ligand, (CpiPr4)Ru(CO)2H (CpiPr4 = C5(i-C3H7)4H) was prepared from the reaction of Ru3(CO)12 with 1,2,3,4-tetraisopropylcyclopentadiene. The molecular structure of (CpiPr4)Ru(CO)2H was determined by x-ray crystallography. The ruthenium hydride complex (C5Bz5)Ru(CO)2H (Bz = CH2Ph) was similarly prepared. The Ru-Ru bonded dimer, [(1,2,3-trimethylindenyl)Ru(CO)2]2, was produced from the reaction of 1,2,3-trimethylindene with Ru3(CO)12, and protonation of this dimer with HOTf gives {[(1,2,3-trimethylindenyl)Ru(CO)2]2(μ H)}+OTf –. A series of ruthenium hydride complexes CpRu(CO)(L)H [L = P(OPh)3, PCy3, PMe3, P(p C6H4F)3] were prepared by reaction of Cp(CO)2RuH with added L. Protonation of (CpiPr4)Ru(CO)2H, Cp*Ru(CO)2H or CpRu(CO)[P(OPh)3]H by HOTf 80more » °C led to equilibria with the cationic dihydrogen complexes, but H2 was released at higher temperatures. Protonation of CpRu[P(OPh)3]2H with HOTf gave an observable dihydrogen complex, {CpRu[P(OPh)3]2(η2 H2)}+OTf – that was converted at -20 °C to the dihydride complex {CpRu[P(OPh)3]2(H)2}+OTf –. These Ru complexes serve as catalyst precursors for the catalytic deoxygenation of 1,2-propanediol to give n-propanol. The catalytic reactions were carried out in sulfolane solvent with added HOTf under H2 (750 psi) at 110 °C. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. Pacific Northwest National Laboratory is operated by Battelle for DOE.« less
  • New mixed-ligand chelates with the formula (Ru(bipy)(PP)YX)/sup n+/ (bipy stands for 2,2'-bipyridyl; PP stands for 1,2-bis(diphenylphosphino)ethane and cis-1,2,-bis-(diphenylphosphino)ethylene; Y = CO (n = 1), NO (n = 2); X = Cl, Br, I) have been synthesized. The compounds have been obtained in the form of the two possible isomers with cis structures. It has been shown that the isomers of the complexes containing a CO or NO ligand in the trans position to a phosphorus atom of the diphosphine are thermally unstable, and at elevated temperatures they undergo exothermic cis-cis isomerization with migration of the ligand with a multiple bondmore » to the transposition to a bipyridyl nitrogen atom in the solid phase. A process of thermal decarbonylation has been discovered in solutions of the carbonyl complexes with a CO ligand in a trans position to the phosphine, and the occurrence of reversible bonding of carbon monoxide by the complexes cis-(Ru(bipy)(PP)X/sub 2/) has been established. The complexes have been characterized by data from elemental analysis, IR and /sup 31/P NMR spectroscopy, and cyclic voltammetry. It has been shown that the chelating phosphine increases the electrophilic activity of the /RuCO//sup 2 +/ fragment to a considerable extent and lowers the reductive stability of the /RuNO//sup 3 +/ fragment.« less
  • The synthesis and spectroscopic properties of ether-phosphine ruthenium(II) complexes of the type Cl[sub 2]Ru([cflx P O])[sub 2] (5a, 7a-10a) and trans-Cl[sub 2]Ru(CO)(P[approximately]O)([cflx P O]) (5b, 7b-10b) are reported. Temperature-dependent [sup 31]P NMR spectra of the fluxional complexes 1b-11b and cis-Cl[sub 2]Ru(CO)(P[approximately]O)([cflx P O]) (1c-3c) were measured and by using a modified version of DNMR5, computer-generated spectra were obtained and fitted to the experimental spectra. Graphic application of the Eyring equation to the kinetic data afforded the thermodynamic parameters [Delta]H[double dagger], [Delta]S[double dagger], and [Delta]G[double dagger]. Complex 11b with the strong basic four-membered ether-phosphine 11 crystallizes in the monoclinic space groupmore » P2[sub 1]/n, with a = 11.974(2) [Angstrom], b = 10.877(2) [Angstrom], c = 29.567(6) [Angstrom], [beta] = 96.34(3)[degrees], Z = 4, and V = 3827.2(12) [Angstrom][sup 3] (R = 0.075 and R[sub w] = 0.076). 33 refs., 4 figs., 4 tabs.« less
  • The reaction of Ru{sub 4}(CO){sub 13}({mu}-H){sub 2} (1) with Pt(COD){sub 2} at 25 C yielded four new platinum-ruthenium carbonyl cluster complexes Ru{sub 4}Pt(CO){sub 13}(COD)({mu}-H){sub 2} (2) (37%), Ru{sub 3}Pt(CO){sub 9}({mu}-CO)(COD)({mu}-H){sub 2} (3) (10%), Ru{sub 4}Pt{sub 2}-(CO){sub 11}(COD){sub 2}({mu}{sub 3}-H){sub 2} (4) (2.5%), and Ru{sub 5}Pt{sub 5}(CO){sub 18}(COD){sub 2}({mu}{sub 3}-H){sub 2} (5) (1%). All compounds were characterized by IR, {sup 1}H NMR, and single-crystal X-ray diffraction analyses. The cluster of compound 2 consists of a butterfly tetrahedron of four ruthenium atoms with one triangular face capped by a Pt(COD) grouping. Compound 3 consists of a cluster of three ruthenium atoms andmore » one platinum atom in a tetrahedral arrangement. Compound 4 consists of a tetrahedral cluster of four ruthenium atoms with two of the triangular faces capped by Pt(COD) groupings. The other two triangular faces have triply bridging hydride ligands. In the cluster of compound 5, the five ruthenium and four of the platinum atoms are arranged in the form of a face-shared bioctahedron. The shared face consists of three of the platinum atoms. The fifth platinum atom is a cap on one of the Ru{sub 2}Pt triangles. Two hydride ligands are believed to bridge metals of the triangular faces on the opposite ends of the bioctahedron.« less
  • 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, asmore » 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.« less