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Article: Ruthenium Carbene and Allenylidene Complexes Supported by the Tertiary Amine-Aromatic Diimine Ligand Set: Structural, Spectroscopic, and Theoretical Studies

TitleRuthenium Carbene and Allenylidene Complexes Supported by the Tertiary Amine-Aromatic Diimine Ligand Set: Structural, Spectroscopic, and Theoretical Studies
Authors
KeywordsAmines
Charge transfer
Chemical bonds
Chromium compounds
Density functional theory
Ion exchange
Ligands
Ruthenium
Issue Date2008
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
Citation
Organometallics, 2008, v. 27 n. 22, p. 5806-5814 How to Cite?
AbstractRuthenium−methoxycarbene and −allenylidene complexes bearing 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3Tacn) and 1,10-phenanthroline (phen), [(Me3Tacn)(phen)Ru═C(OMe)R]2+ (R = CH2Ph (1), CH═CPh2 (2), CH═C(C6H4Cl-4)2 (3), CH═C(C6H4Me-4)2 (4)), and [(Me3Tacn)(phen)Ru═C═C═CR2]2+ (R = Ph (5), C6H4OMe-4 (6)) have been prepared. The molecular structures of 1(PF6)2 and 2(PF6)2 reveal Ru−C distances of 1.917(3) and 1.906(4) Å, respectively. The lowest-energy dipole-allowed absorptions for complexes 1−4 (λmax ≈ 435 nm) are assigned as dπ(RuII) → π*(phen) metal-to-ligand charge transfer (MLCT) transitions, while those for complexes 5 and 6 (λmax = 530 and 585 nm, respectively) are assigned as metal-perturbed π−π* [Ru═C═C═CR2] intraligand transitions. Complexes 1−4 are emissive in glassy MeOH/EtOH at 77 K: excitation at λ = 430 nm produces emission at λmax = 570−620 nm, which are tentatively assigned as dπ(RuII) → π*(phen) 3MLCT in nature. Density functional theory (DFT) calculations, charge decomposition analysis (CDA), and natural bond orbital (NBO) analysis on complexes 1, 2, 5, and 6 suggest that allenylidene ligands are better electron donors and poorer acceptors compared with methoxycarbene ligands, and the Ru−C interactions in ruthenium−allenylidene and −methoxycarbene complexes can be depicted by the polarized formulation Ruδ+═Cδ− and nonpolarized formulation Ru═C, respectively. The methoxycarbene/allenylidene rotational barriers on 1, 2, and 5 are calculated to be 8.3, 6.3, and 1.5 kcal mol−1, respectively.
Persistent Identifierhttp://hdl.handle.net/10722/58349
ISSN
2015 Impact Factor: 4.186
2015 SCImago Journal Rankings: 2.043
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorWong, CYen_HK
dc.contributor.authorLai, LMen_HK
dc.contributor.authorLam, CYen_HK
dc.contributor.authorZhu, Nen_HK
dc.date.accessioned2010-05-31T03:28:45Z-
dc.date.available2010-05-31T03:28:45Z-
dc.date.issued2008en_HK
dc.identifier.citationOrganometallics, 2008, v. 27 n. 22, p. 5806-5814en_HK
dc.identifier.issn0276-7333en_HK
dc.identifier.urihttp://hdl.handle.net/10722/58349-
dc.description.abstractRuthenium−methoxycarbene and −allenylidene complexes bearing 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3Tacn) and 1,10-phenanthroline (phen), [(Me3Tacn)(phen)Ru═C(OMe)R]2+ (R = CH2Ph (1), CH═CPh2 (2), CH═C(C6H4Cl-4)2 (3), CH═C(C6H4Me-4)2 (4)), and [(Me3Tacn)(phen)Ru═C═C═CR2]2+ (R = Ph (5), C6H4OMe-4 (6)) have been prepared. The molecular structures of 1(PF6)2 and 2(PF6)2 reveal Ru−C distances of 1.917(3) and 1.906(4) Å, respectively. The lowest-energy dipole-allowed absorptions for complexes 1−4 (λmax ≈ 435 nm) are assigned as dπ(RuII) → π*(phen) metal-to-ligand charge transfer (MLCT) transitions, while those for complexes 5 and 6 (λmax = 530 and 585 nm, respectively) are assigned as metal-perturbed π−π* [Ru═C═C═CR2] intraligand transitions. Complexes 1−4 are emissive in glassy MeOH/EtOH at 77 K: excitation at λ = 430 nm produces emission at λmax = 570−620 nm, which are tentatively assigned as dπ(RuII) → π*(phen) 3MLCT in nature. Density functional theory (DFT) calculations, charge decomposition analysis (CDA), and natural bond orbital (NBO) analysis on complexes 1, 2, 5, and 6 suggest that allenylidene ligands are better electron donors and poorer acceptors compared with methoxycarbene ligands, and the Ru−C interactions in ruthenium−allenylidene and −methoxycarbene complexes can be depicted by the polarized formulation Ruδ+═Cδ− and nonpolarized formulation Ru═C, respectively. The methoxycarbene/allenylidene rotational barriers on 1, 2, and 5 are calculated to be 8.3, 6.3, and 1.5 kcal mol−1, respectively.-
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.subjectAmines-
dc.subjectCharge transfer-
dc.subjectChemical bonds-
dc.subjectChromium compounds-
dc.subjectDensity functional theory-
dc.subjectIon exchange-
dc.subjectLigands-
dc.subjectRuthenium-
dc.titleRuthenium Carbene and Allenylidene Complexes Supported by the Tertiary Amine-Aromatic Diimine Ligand Set: Structural, Spectroscopic, and Theoretical Studiesen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0276-7333&volume=27&spage=5806&epage=5814&date=2008&atitle=Ruthenium+Carbene+and+Allenylidene+Complexes+Supported+by+the+Tertiary+Amine#Aromatic+Diimine+Ligand+Set: Sturctural,+Spectroscopic,+and+Theoretical+Studiesen_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.doi10.1021/om800592a-
dc.identifier.scopuseid_2-s2.0-57049152939-
dc.identifier.hkuros155701en_HK
dc.identifier.volume27-
dc.identifier.issue22-
dc.identifier.spage5806-
dc.identifier.epage5814-
dc.identifier.isiWOS:000260791400040-

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