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Article: The metal-carbon stretching frequencies in methyl complexes of Rh, Ir, Ga and In with porphyrins and a tetradentate pyridine-amide ligand

TitleThe metal-carbon stretching frequencies in methyl complexes of Rh, Ir, Ga and In with porphyrins and a tetradentate pyridine-amide ligand
Authors
KeywordsBpb, 1,2-bis
FT-Raman spectroscopy
Metal methyl compounds
Metal-carbon stretching frequency
OEP, 2,3,7,8,12,13,17,18-octaethylporphyrin dianion
Por, porphyrin dianion
Trans ligand effect
TTP, 5,10,15,20-tetrakis(4-methylphenyl)porphyrin dianion
Issue Date2001
PublisherElsevier SA. The Journal's web site is located at http://www.elsevier.com/locate/jorganchem
Citation
Journal Of Organometallic Chemistry, 2001, v. 634 n. 1, p. 61-68 How to Cite?
AbstractInteractions of trans-[Rh(bpb)(CH3)(H2O)] (1) [bpb=1,2-bis(2-pyridinecarboxamido)benzene] with Lewis bases L afford the respective adducts trans-[Rh(bpb)(CH3)(L)], where L=4-substituted pyridine 4-Xpy (X=H (2), tBu (3), NMe2 (4) CN (5)), PMe2Ph (6) or benzimidazole (7). The structures of complexes 3 and 6 have been established by X-ray crystallography. The Rh-C distance in complex 6 (2.095(6) Å) is longer than that in complex 3 (2.02(1) Å), indicating that PMe2Ph has a stronger trans influence than 4-tBupy. The metal-carbon stretching frequencies for trans-[Rh(bpb)(CH3)(L)] and [M(TTP)(CH3)] [TTP=5,10,15,20-tetrakis(4-methylphenyl)porphyrin dianion; M=Rh, Ir, Ga, In] have been determined by near IR FT-Raman spectroscopy. Complex 1 exhibits ν(Rh-C) at 562 cm-1, which downshifts to 532 cm-1 upon deuteriation of the axial methyl group. Replacement of the aquo ligand in complex 1 with nitrogen ligands or phosphine resulted in downshift in ν(Rh-C). The ν(Rh-C) for trans-[Rh(bpb)(CH3)(L)] was found to decrease in the order L: PMe2Ph≫4-Xpy~BzIm>H2O, consistent the order of trans influence of L. For [M(TTP)(CH3)] (M=Co, Rh, Ir, Ga, or In) the M-C force constant was found to decrease in the orders Ir>Rh>Co and Ga>In, consistent with the trends of metal-carbon bond strength for these metals. For trans-[Rh(bpb)(CH3)(4-Xpy)] and trans-[Rh(TTP)(CH3)(4-Xpy)], the ν(Rh-C) were found to be not very sensitive to the nature of X, suggesting that the electronic factors of the axial pyridine ligand do not have a significant effect on the Rh-C bonds for these rhodium alkyl complexes.
Persistent Identifierhttp://hdl.handle.net/10722/69055
ISSN
2015 Impact Factor: 2.336
2015 SCImago Journal Rankings: 0.732
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLai, Wen_HK
dc.contributor.authorLau, MKen_HK
dc.contributor.authorChong, Ven_HK
dc.contributor.authorWong, WTen_HK
dc.contributor.authorLeung, WHen_HK
dc.contributor.authorYu, NTen_HK
dc.date.accessioned2010-09-06T06:10:08Z-
dc.date.available2010-09-06T06:10:08Z-
dc.date.issued2001en_HK
dc.identifier.citationJournal Of Organometallic Chemistry, 2001, v. 634 n. 1, p. 61-68en_HK
dc.identifier.issn0022-328Xen_HK
dc.identifier.urihttp://hdl.handle.net/10722/69055-
dc.description.abstractInteractions of trans-[Rh(bpb)(CH3)(H2O)] (1) [bpb=1,2-bis(2-pyridinecarboxamido)benzene] with Lewis bases L afford the respective adducts trans-[Rh(bpb)(CH3)(L)], where L=4-substituted pyridine 4-Xpy (X=H (2), tBu (3), NMe2 (4) CN (5)), PMe2Ph (6) or benzimidazole (7). The structures of complexes 3 and 6 have been established by X-ray crystallography. The Rh-C distance in complex 6 (2.095(6) Å) is longer than that in complex 3 (2.02(1) Å), indicating that PMe2Ph has a stronger trans influence than 4-tBupy. The metal-carbon stretching frequencies for trans-[Rh(bpb)(CH3)(L)] and [M(TTP)(CH3)] [TTP=5,10,15,20-tetrakis(4-methylphenyl)porphyrin dianion; M=Rh, Ir, Ga, In] have been determined by near IR FT-Raman spectroscopy. Complex 1 exhibits ν(Rh-C) at 562 cm-1, which downshifts to 532 cm-1 upon deuteriation of the axial methyl group. Replacement of the aquo ligand in complex 1 with nitrogen ligands or phosphine resulted in downshift in ν(Rh-C). The ν(Rh-C) for trans-[Rh(bpb)(CH3)(L)] was found to decrease in the order L: PMe2Ph≫4-Xpy~BzIm>H2O, consistent the order of trans influence of L. For [M(TTP)(CH3)] (M=Co, Rh, Ir, Ga, or In) the M-C force constant was found to decrease in the orders Ir>Rh>Co and Ga>In, consistent with the trends of metal-carbon bond strength for these metals. For trans-[Rh(bpb)(CH3)(4-Xpy)] and trans-[Rh(TTP)(CH3)(4-Xpy)], the ν(Rh-C) were found to be not very sensitive to the nature of X, suggesting that the electronic factors of the axial pyridine ligand do not have a significant effect on the Rh-C bonds for these rhodium alkyl complexes.en_HK
dc.languageengen_HK
dc.publisherElsevier SA. The Journal's web site is located at http://www.elsevier.com/locate/jorganchemen_HK
dc.relation.ispartofJournal of Organometallic Chemistryen_HK
dc.subjectBpb, 1,2-bisen_HK
dc.subjectFT-Raman spectroscopyen_HK
dc.subjectMetal methyl compoundsen_HK
dc.subjectMetal-carbon stretching frequencyen_HK
dc.subjectOEP, 2,3,7,8,12,13,17,18-octaethylporphyrin dianionen_HK
dc.subjectPor, porphyrin dianionen_HK
dc.subjectTrans ligand effecten_HK
dc.subjectTTP, 5,10,15,20-tetrakis(4-methylphenyl)porphyrin dianionen_HK
dc.titleThe metal-carbon stretching frequencies in methyl complexes of Rh, Ir, Ga and In with porphyrins and a tetradentate pyridine-amide liganden_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0022-328X&volume=634&spage=61&epage=68&date=2001&atitle=The+metal-carbon+stretching+frequencies+in+methyl+complexes+of+Rh,+Ir,+Ga+and+In+with+porphyrins+and+a+tetradentate+pyridine-amide+liganden_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1016/S0022-328X(01)01097-Xen_HK
dc.identifier.scopuseid_2-s2.0-0038823081en_HK
dc.identifier.hkuros68321en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0038823081&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume634en_HK
dc.identifier.issue1en_HK
dc.identifier.spage61en_HK
dc.identifier.epage68en_HK
dc.identifier.isiWOS:000171400300010-
dc.publisher.placeSwitzerlanden_HK
dc.identifier.scopusauthoridLai, W=36790429700en_HK
dc.identifier.scopusauthoridLau, MK=7102344959en_HK
dc.identifier.scopusauthoridChong, V=7004645685en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK
dc.identifier.scopusauthoridLeung, WH=7201504510en_HK
dc.identifier.scopusauthoridYu, NT=7201983280en_HK

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