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Article: Intramolecular N-H...H-Ru proton-hydride interaction in ruthenium complexes with (2-(dimethylamino)ethyl)cyclopentadienyl and (3-(dimethylamino)propyl)cyclopentadienyl ligands. Hydrogenation of CO2 to formic acid via the N-H...H-Ru hydrogen-bonded complexes

TitleIntramolecular N-H...H-Ru proton-hydride interaction in ruthenium complexes with (2-(dimethylamino)ethyl)cyclopentadienyl and (3-(dimethylamino)propyl)cyclopentadienyl ligands. Hydrogenation of CO2 to formic acid via the N-H...H-Ru hydrogen-bonded complexes
Authors
Issue Date1998
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
Citation
Organometallics, 1998, v. 17 n. 13, p. 2768-2777 How to Cite?
AbstractAddition of 1 equiv of HBF4 to (η5-C5H4(CH2)nNMe2)RuH(dppm) (n = 2, 3) gave [(η5-C5H4(CH2)nNMe2H+)RuH(dppm)]BF4, in which the amine function was protonated. Relaxation time T1 measurements indicated the existence of an intramolecular N−H···H−Ru hydrogen-bonding interaction in these complexes. A spin saturation transfer study and H/D exchange experiment with [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BF4 revealed fast exchange, probably via a dihydrogen complex intermediate, between the hydride ligand and N−H. An attempt to grow single crystals of [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BPh4 for X-ray study resulted in isolation of crystals of the complex, [(η5:η1-C5H4(CH2)3NMe2)Ru(dppm)]BPh4, with the chelating (3-(dimethylamino)propyl)cyclopentadienyl ligand. Exposure of [(η5:η1-C5H4(CH2)3NMe2)Ru(dppm)]BF4 to 60 atm of H2 at 60 °C gave [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BF4 within 30 min. Reacting [(η5:η1-C5H4(CH2)3NMe2)Ru(dppm)]BAr‘4 (Ar‘ = 3,5-(CF3)2C6H3) with Ph2SiH2 yielded [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BAr‘4; it is proposed that hydrolysis of the η2-silane intermediate by adventitious moisture in the solvent affords an η2-dihydrogen species, and heterolytic cleavage of the dihydrogen ligand by the pendant amino group gives the final product. Heating solutions of [(η5:η1-C5H4(CH2)nNMe2)Ru(dppm)]BF4 under H2/CO2 (40 atm/40 atm) at 80 °C for 16 h gave formic acid in low yields (n = 2, TON = 6; n = 3, TON = 8). The formation of formic acid is best explained by a mechanism involving intramolecular heterolytic cleavage of the bound H2 to generate [(η5-C5H4(CH2)nNMe2H+)RuH(dppm)]BF4, followed by CO2 insertion into the Ru−H and then N−H protonation of the formato ligand. Carbon disulfide inserted into the Ru−H bond of [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BF4 to give [(η5-C5H4(CH2)3NMe2H+)Ru(η1-SCSH)(dppm)]BF4.
Persistent Identifierhttp://hdl.handle.net/10722/69392
ISSN
2015 Impact Factor: 4.186
2015 SCImago Journal Rankings: 2.043
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorChu, HSen_HK
dc.contributor.authorLau, CPen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:13:14Z-
dc.date.available2010-09-06T06:13:14Z-
dc.date.issued1998en_HK
dc.identifier.citationOrganometallics, 1998, v. 17 n. 13, p. 2768-2777en_HK
dc.identifier.issn0276-7333en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69392-
dc.description.abstractAddition of 1 equiv of HBF4 to (η5-C5H4(CH2)nNMe2)RuH(dppm) (n = 2, 3) gave [(η5-C5H4(CH2)nNMe2H+)RuH(dppm)]BF4, in which the amine function was protonated. Relaxation time T1 measurements indicated the existence of an intramolecular N−H···H−Ru hydrogen-bonding interaction in these complexes. A spin saturation transfer study and H/D exchange experiment with [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BF4 revealed fast exchange, probably via a dihydrogen complex intermediate, between the hydride ligand and N−H. An attempt to grow single crystals of [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BPh4 for X-ray study resulted in isolation of crystals of the complex, [(η5:η1-C5H4(CH2)3NMe2)Ru(dppm)]BPh4, with the chelating (3-(dimethylamino)propyl)cyclopentadienyl ligand. Exposure of [(η5:η1-C5H4(CH2)3NMe2)Ru(dppm)]BF4 to 60 atm of H2 at 60 °C gave [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BF4 within 30 min. Reacting [(η5:η1-C5H4(CH2)3NMe2)Ru(dppm)]BAr‘4 (Ar‘ = 3,5-(CF3)2C6H3) with Ph2SiH2 yielded [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BAr‘4; it is proposed that hydrolysis of the η2-silane intermediate by adventitious moisture in the solvent affords an η2-dihydrogen species, and heterolytic cleavage of the dihydrogen ligand by the pendant amino group gives the final product. Heating solutions of [(η5:η1-C5H4(CH2)nNMe2)Ru(dppm)]BF4 under H2/CO2 (40 atm/40 atm) at 80 °C for 16 h gave formic acid in low yields (n = 2, TON = 6; n = 3, TON = 8). The formation of formic acid is best explained by a mechanism involving intramolecular heterolytic cleavage of the bound H2 to generate [(η5-C5H4(CH2)nNMe2H+)RuH(dppm)]BF4, followed by CO2 insertion into the Ru−H and then N−H protonation of the formato ligand. Carbon disulfide inserted into the Ru−H bond of [(η5-C5H4(CH2)3NMe2H+)RuH(dppm)]BF4 to give [(η5-C5H4(CH2)3NMe2H+)Ru(η1-SCSH)(dppm)]BF4.-
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallicsen_HK
dc.relation.ispartofOrganometallicsen_HK
dc.titleIntramolecular N-H...H-Ru proton-hydride interaction in ruthenium complexes with (2-(dimethylamino)ethyl)cyclopentadienyl and (3-(dimethylamino)propyl)cyclopentadienyl ligands. Hydrogenation of CO2 to formic acid via the N-H...H-Ru hydrogen-bonded complexesen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0276-7333&volume=17&spage=2768&epage=2777&date=1998&atitle=Intramolecular+N-H...H-Ru+proton-hydride+interaction+in+ruthenium+complexes+with+(2-(dimethylamino)ethyl)cyclopentadienyl+and+(3-(dimethylamino)propyl)cyclopentadienyl+ligands.++Hydrogenation+of+CO2+to+formic+acid+via+the+N-H...H-Ru+hydrogen-ben_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.identifier.doi10.1021/om980071v-
dc.identifier.hkuros32606en_HK
dc.identifier.volume17-
dc.identifier.issue13-
dc.identifier.spage2768-
dc.identifier.epage2777-
dc.identifier.isiWOS:000074448800016-
dc.publisher.placeUnited States-

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