Oligophosphan-Liganden

Synthesis and Properties of the Indenyl Ruthenium(II) Complex [Ru{(E)-η1-C(C⋮CPh)CHPh}(η5-C9H7)(κ2-P-dppm)] (dppm = bis(diphenylphosphino)methane). An Organometallic Intermediate in the Catalytic Dimerization of Phenylacetylene

“…The preparation of complex 3 via reaction of the hydride complex 1 with diphenylbutadiyne to form σ-butenynyl complexes is not common. These species are obtained by reaction of alkynyl ruthenium derivatives with a terminal alkyne, 1f, by reaction of a vinylidene complex with LiC⋮C t Bu, by protonation of a bis(σ-alkynyl) ruthenium complex and subsequent coupling, or by carbon−carbon coupling in alkynyl-vinylidene complexes . When [Ru(C⋮CPh)(η 5 -C 9 H 7 )(dppm)] is allowed to react with PhC⋮CH in toluene, ( E )- and ( Z )-1,4-diphenyl-1-buten-3-yne form at elevated temperatures as the only organic products, while the alkynyl complex is the only organometallic species observed by 31 P and 1 H NMR, maintaining constant concentration throughout the reaction.…”

“…This implies rate-limiting reaction of the alkynyl with the alkyne followed by fast σ-metathesis with a second alkyne molecule to form the organic products, the presumed σ-enynyl complex not being detectable (Scheme ). In the case of [Ru(PP 3 )(C⋮CSiMe 3 )][BF 4 ] reacting with Me 3 SiC⋮CH,1f or of [Ru(C⋮CPh)Tp(κ 2 (P,O)-Ph 2 PCH 2 CH 2 OMe)] reacting with PhC⋮CH, η 3 -butenynyl complexes are stable and isolable materials. It is possible that such enynyl complexes via this route are stabilized by the η 3 -coordination mode, which is allowed by the four-donor system (P 4 ) in one case 1f and by the hemilabile character of the phosphinoether ligand in the other …”

“…Conversely, the η 3 -enynyl complexes [(PP 3 )Ru{( E )-η 3 -C(C⋮CR)CHR}]BF 4 (R = SiMe 3 , Ph) were the only organometallic species observable in the course of the catalytic dimerization of RC⋮CH by [Ru(σ-C⋮CR)(PP 3 )] 1f…”

Synthesis and Properties of the Indenyl Ruthenium(II) Complex [Ru{(E)-η1-C(C⋮CPh)CHPh}(η5-C9H7)(κ2-P-dppm)] (dppm = bis(diphenylphosphino)methane). An Organometallic Intermediate in the Catalytic Dimerization of Phenylacetylene

“…The preparation of complex 3 via reaction of the hydride complex 1 with diphenylbutadiyne to form σ-butenynyl complexes is not common. These species are obtained by reaction of alkynyl ruthenium derivatives with a terminal alkyne, 1f, by reaction of a vinylidene complex with LiC⋮C t Bu, by protonation of a bis(σ-alkynyl) ruthenium complex and subsequent coupling, or by carbon−carbon coupling in alkynyl-vinylidene complexes . When [Ru(C⋮CPh)(η 5 -C 9 H 7 )(dppm)] is allowed to react with PhC⋮CH in toluene, ( E )- and ( Z )-1,4-diphenyl-1-buten-3-yne form at elevated temperatures as the only organic products, while the alkynyl complex is the only organometallic species observed by 31 P and 1 H NMR, maintaining constant concentration throughout the reaction.…”

“…This implies rate-limiting reaction of the alkynyl with the alkyne followed by fast σ-metathesis with a second alkyne molecule to form the organic products, the presumed σ-enynyl complex not being detectable (Scheme ). In the case of [Ru(PP 3 )(C⋮CSiMe 3 )][BF 4 ] reacting with Me 3 SiC⋮CH,1f or of [Ru(C⋮CPh)Tp(κ 2 (P,O)-Ph 2 PCH 2 CH 2 OMe)] reacting with PhC⋮CH, η 3 -butenynyl complexes are stable and isolable materials. It is possible that such enynyl complexes via this route are stabilized by the η 3 -coordination mode, which is allowed by the four-donor system (P 4 ) in one case 1f and by the hemilabile character of the phosphinoether ligand in the other …”

“…Conversely, the η 3 -enynyl complexes [(PP 3 )Ru{( E )-η 3 -C(C⋮CR)CHR}]BF 4 (R = SiMe 3 , Ph) were the only organometallic species observable in the course of the catalytic dimerization of RC⋮CH by [Ru(σ-C⋮CR)(PP 3 )] 1f…”

Formic acid dehydrogenation catalysed by ruthenium complexes bearing the tripodal ligands triphos and NP 3

“…Complexes 1 and 2 were prepared according to literature procedures. 12,13 Formic acid and N,N-dimethyloctylamine were The formic acid to amine ratio was determined by 1 H NMR spectroscopy on a Bruker Avance 400 spectrometer. Ru(acac) 3 and the HCOOH-NEt 3 (5 : 2) mixture were purchased from commercial suppliers and used without further purification.…”

cis-Dichloro[tris(diphenylphosphinoethyl)amine]ruthenium(II)–chloroform–water (1/2.5/1)

“…The title compound, (I), displays interesting catalytic properties, as shown by Fontal & Suarez (1985) in the case of hydrogenation and hydroformylation, as well as others (Dahlenbourg et al, 1991), in 1-alkyne dimerization reactions, but in spite of a good spectroscopic characterization, especially through 1 H and 31 P NMR spectroscopic analyses, the crystal structure of (I) is hitherto unreported.…”

Synthesis and Properties of the Indenyl Ruthenium(II) Complex [Ru{(E)-η1-C(C⋮CPh)CHPh}(η5-C9H7)(κ2-P-dppm)] (dppm = bis(diphenylphosphino)methane). An Organometallic Intermediate in the Catalytic Dimerization of Phenylacetylene

“…The preparation of complex 3 via reaction of the hydride complex 1 with diphenylbutadiyne to form σ-butenynyl complexes is not common. These species are obtained by reaction of alkynyl ruthenium derivatives with a terminal alkyne, 1f, by reaction of a vinylidene complex with LiC⋮C t Bu, by protonation of a bis(σ-alkynyl) ruthenium complex and subsequent coupling, or by carbon−carbon coupling in alkynyl-vinylidene complexes . When [Ru(C⋮CPh)(η 5 -C 9 H 7 )(dppm)] is allowed to react with PhC⋮CH in toluene, ( E )- and ( Z )-1,4-diphenyl-1-buten-3-yne form at elevated temperatures as the only organic products, while the alkynyl complex is the only organometallic species observed by 31 P and 1 H NMR, maintaining constant concentration throughout the reaction.…”

“…This implies rate-limiting reaction of the alkynyl with the alkyne followed by fast σ-metathesis with a second alkyne molecule to form the organic products, the presumed σ-enynyl complex not being detectable (Scheme ). In the case of [Ru(PP 3 )(C⋮CSiMe 3 )][BF 4 ] reacting with Me 3 SiC⋮CH,1f or of [Ru(C⋮CPh)Tp(κ 2 (P,O)-Ph 2 PCH 2 CH 2 OMe)] reacting with PhC⋮CH, η 3 -butenynyl complexes are stable and isolable materials. It is possible that such enynyl complexes via this route are stabilized by the η 3 -coordination mode, which is allowed by the four-donor system (P 4 ) in one case 1f and by the hemilabile character of the phosphinoether ligand in the other …”

“…Conversely, the η 3 -enynyl complexes [(PP 3 )Ru{( E )-η 3 -C(C⋮CR)CHR}]BF 4 (R = SiMe 3 , Ph) were the only organometallic species observable in the course of the catalytic dimerization of RC⋮CH by [Ru(σ-C⋮CR)(PP 3 )] 1f…”

Formic acid dehydrogenation catalysed by ruthenium complexes bearing the tripodal ligands triphos and NP 3

“…Complexes 1 and 2 were prepared according to literature procedures. 12,13 Formic acid and N,N-dimethyloctylamine were The formic acid to amine ratio was determined by 1 H NMR spectroscopy on a Bruker Avance 400 spectrometer. Ru(acac) 3 and the HCOOH-NEt 3 (5 : 2) mixture were purchased from commercial suppliers and used without further purification.…”

cis-Dichloro[tris(diphenylphosphinoethyl)amine]ruthenium(II)–chloroform–water (1/2.5/1)

“…The title compound, (I), displays interesting catalytic properties, as shown by Fontal & Suarez (1985) in the case of hydrogenation and hydroformylation, as well as others (Dahlenbourg et al, 1991), in 1-alkyne dimerization reactions, but in spite of a good spectroscopic characterization, especially through 1 H and 31 P NMR spectroscopic analyses, the crystal structure of (I) is hitherto unreported.…”

Synthesis and Properties of the Indenyl Ruthenium(II) Complex [Ru{(E)-η1-C(C⋮CPh)CHPh}(η5-C9H7)(κ2-P-dppm)] (dppm = bis(diphenylphosphino)methane). An Organometallic Intermediate in the Catalytic Dimerization of Phenylacetylene

“…The preparation of complex 3 via reaction of the hydride complex 1 with diphenylbutadiyne to form σ-butenynyl complexes is not common. These species are obtained by reaction of alkynyl ruthenium derivatives with a terminal alkyne, 1f, by reaction of a vinylidene complex with LiC⋮C t Bu, by protonation of a bis(σ-alkynyl) ruthenium complex and subsequent coupling, or by carbon−carbon coupling in alkynyl-vinylidene complexes . When [Ru(C⋮CPh)(η 5 -C 9 H 7 )(dppm)] is allowed to react with PhC⋮CH in toluene, ( E )- and ( Z )-1,4-diphenyl-1-buten-3-yne form at elevated temperatures as the only organic products, while the alkynyl complex is the only organometallic species observed by 31 P and 1 H NMR, maintaining constant concentration throughout the reaction.…”

“…This implies rate-limiting reaction of the alkynyl with the alkyne followed by fast σ-metathesis with a second alkyne molecule to form the organic products, the presumed σ-enynyl complex not being detectable (Scheme ). In the case of [Ru(PP 3 )(C⋮CSiMe 3 )][BF 4 ] reacting with Me 3 SiC⋮CH,1f or of [Ru(C⋮CPh)Tp(κ 2 (P,O)-Ph 2 PCH 2 CH 2 OMe)] reacting with PhC⋮CH, η 3 -butenynyl complexes are stable and isolable materials. It is possible that such enynyl complexes via this route are stabilized by the η 3 -coordination mode, which is allowed by the four-donor system (P 4 ) in one case 1f and by the hemilabile character of the phosphinoether ligand in the other …”

“…Conversely, the η 3 -enynyl complexes [(PP 3 )Ru{( E )-η 3 -C(C⋮CR)CHR}]BF 4 (R = SiMe 3 , Ph) were the only organometallic species observable in the course of the catalytic dimerization of RC⋮CH by [Ru(σ-C⋮CR)(PP 3 )] 1f…”

Formic acid dehydrogenation catalysed by ruthenium complexes bearing the tripodal ligands triphos and NP 3

“…Complexes 1 and 2 were prepared according to literature procedures. 12,13 Formic acid and N,N-dimethyloctylamine were The formic acid to amine ratio was determined by 1 H NMR spectroscopy on a Bruker Avance 400 spectrometer. Ru(acac) 3 and the HCOOH-NEt 3 (5 : 2) mixture were purchased from commercial suppliers and used without further purification.…”

cis-Dichloro[tris(diphenylphosphinoethyl)amine]ruthenium(II)–chloroform–water (1/2.5/1)

“…The title compound, (I), displays interesting catalytic properties, as shown by Fontal & Suarez (1985) in the case of hydrogenation and hydroformylation, as well as others (Dahlenbourg et al, 1991), in 1-alkyne dimerization reactions, but in spite of a good spectroscopic characterization, especially through 1 H and 31 P NMR spectroscopic analyses, the crystal structure of (I) is hitherto unreported.…”