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Article: Probing the Ruthenium-Cumulene Bonding Interaction: Synthesis and Spectroscopic Studies of Vinylidene- and Allenylidene-Ruthenium Complexes Supported by Tetradentate Macrocyclic Tertiary Amine and Comparisons with Diphosphine Analogues of Ruthenium and Osmium

TitleProbing the Ruthenium-Cumulene Bonding Interaction: Synthesis and Spectroscopic Studies of Vinylidene- and Allenylidene-Ruthenium Complexes Supported by Tetradentate Macrocyclic Tertiary Amine and Comparisons with Diphosphine Analogues of Ruthenium and Osmium
Authors
Issue Date2004
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
Citation
Journal Of The American Chemical Society, 2004, v. 126 n. 8, p. 2501-2514 How to Cite?
AbstractThe synthesis and spectroscopic properties of trans-[Cl(16-TMC)Ru=C=CHR]PF6 (16-TMC = 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane, R = C6H 4X-4, X = H (1), Cl (2), Me (3), OMe (4); R = CHPh2 (5)), trans-[Cl(16-TMC)Ru=C=C=C(C6H4X-4)2]PF 6 (X = H (6), Cl (7), Me (8), OMe (9)), and trans-[Cl(dppm) 2M=C=C=C(C6H4X-4)2]PF6 (M = Ru, X = H (10), Cl (11), Me (12); M = Os, X = H (13), Cl (14), Me (15)) are described. The crystal structures of 1, 5, 6, and 8 show that the Ru-C α and Cα-Cβ distances of the allenylidene complexes fall between those of the vinylidene and acetylide relatives. Two reversible redox couples are observed by cyclic voltammetry for 6-9, with E1/2 values ranging from -1.19 to -1.42 and 0.49 to 0.70 V vs Cp2Fe+/0, and they are both 0.2-0.3 and 0.1-0.2 V more reducing than those for 10-12 and 13-15, respectively. The UV-vis spectra of the vinylidene complexes 1-4 are dominated by intense high-energy bands at λmax ≤ 310 nm (εmax ≥ 104 dm3 mol-1 cm-1), while weak absorptions at λmax ≥ 400 nm (εmax ≤ 102 dm3 mol-1 cm-1) are tentatively assigned to d-d transitions. The resonance Raman spectrum of 5 contains a nominal v c=c stretch mode of the vinylidene ligand at 1629 cm-1. The electronic absorption spectra of the allenylidene complexes 6-9 exhibit an intense absorption at λmax = 479-513 nm (εmax = (2-3) × 104 dm3 mol-1 cm-1). Similar electronic absorption bands have been found for 10-12, but the lowest energy dipole-allowed transition is blue-shifted by 1530-1830 cm-1 for the Os analogues 13-15. Ab initio calculations have been performed on the ground state of trans-[Cl-(NH3)4Ru=C=C=CPh 2]+ at the MP2 level, and imply that the HOMO is not localized purely on the metal center or allenylidene ligand. The absorption band of 6 at λmax = 479 nm has been probed by resonance Raman spectroscopy. Simulations of the absorption band and the resonance Raman intensities show that the nominal vc=c=c stretch mode accounts for ca. 50% of the total vibrational reorganization energy, indicating that this absorption band is strongly coupled to the allenylidene moiety. The excited-state reorganization of the allenylidene ligand is accompanied by rearrangement of the Ru=C and Ru-N (of 16-TMC) fragments, which supports the existence of bonding interaction between the metal and C=C=C unit in the electronic excited state.
Persistent Identifierhttp://hdl.handle.net/10722/167899
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorWong, CYen_HK
dc.contributor.authorChe, CMen_HK
dc.contributor.authorChan, MCWen_HK
dc.contributor.authorLeung, KHen_HK
dc.contributor.authorPhillips, DLen_HK
dc.contributor.authorZhu, Nen_HK
dc.date.accessioned2012-10-08T03:12:41Z-
dc.date.available2012-10-08T03:12:41Z-
dc.date.issued2004en_HK
dc.identifier.citationJournal Of The American Chemical Society, 2004, v. 126 n. 8, p. 2501-2514en_HK
dc.identifier.issn0002-7863en_HK
dc.identifier.urihttp://hdl.handle.net/10722/167899-
dc.description.abstractThe synthesis and spectroscopic properties of trans-[Cl(16-TMC)Ru=C=CHR]PF6 (16-TMC = 1,5,9,13-tetramethyl-1,5,9,13-tetraazacyclohexadecane, R = C6H 4X-4, X = H (1), Cl (2), Me (3), OMe (4); R = CHPh2 (5)), trans-[Cl(16-TMC)Ru=C=C=C(C6H4X-4)2]PF 6 (X = H (6), Cl (7), Me (8), OMe (9)), and trans-[Cl(dppm) 2M=C=C=C(C6H4X-4)2]PF6 (M = Ru, X = H (10), Cl (11), Me (12); M = Os, X = H (13), Cl (14), Me (15)) are described. The crystal structures of 1, 5, 6, and 8 show that the Ru-C α and Cα-Cβ distances of the allenylidene complexes fall between those of the vinylidene and acetylide relatives. Two reversible redox couples are observed by cyclic voltammetry for 6-9, with E1/2 values ranging from -1.19 to -1.42 and 0.49 to 0.70 V vs Cp2Fe+/0, and they are both 0.2-0.3 and 0.1-0.2 V more reducing than those for 10-12 and 13-15, respectively. The UV-vis spectra of the vinylidene complexes 1-4 are dominated by intense high-energy bands at λmax ≤ 310 nm (εmax ≥ 104 dm3 mol-1 cm-1), while weak absorptions at λmax ≥ 400 nm (εmax ≤ 102 dm3 mol-1 cm-1) are tentatively assigned to d-d transitions. The resonance Raman spectrum of 5 contains a nominal v c=c stretch mode of the vinylidene ligand at 1629 cm-1. The electronic absorption spectra of the allenylidene complexes 6-9 exhibit an intense absorption at λmax = 479-513 nm (εmax = (2-3) × 104 dm3 mol-1 cm-1). Similar electronic absorption bands have been found for 10-12, but the lowest energy dipole-allowed transition is blue-shifted by 1530-1830 cm-1 for the Os analogues 13-15. Ab initio calculations have been performed on the ground state of trans-[Cl-(NH3)4Ru=C=C=CPh 2]+ at the MP2 level, and imply that the HOMO is not localized purely on the metal center or allenylidene ligand. The absorption band of 6 at λmax = 479 nm has been probed by resonance Raman spectroscopy. Simulations of the absorption band and the resonance Raman intensities show that the nominal vc=c=c stretch mode accounts for ca. 50% of the total vibrational reorganization energy, indicating that this absorption band is strongly coupled to the allenylidene moiety. The excited-state reorganization of the allenylidene ligand is accompanied by rearrangement of the Ru=C and Ru-N (of 16-TMC) fragments, which supports the existence of bonding interaction between the metal and C=C=C unit in the electronic excited state.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_HK
dc.relation.ispartofJournal of the American Chemical Societyen_HK
dc.titleProbing the Ruthenium-Cumulene Bonding Interaction: Synthesis and Spectroscopic Studies of Vinylidene- and Allenylidene-Ruthenium Complexes Supported by Tetradentate Macrocyclic Tertiary Amine and Comparisons with Diphosphine Analogues of Ruthenium and Osmiumen_HK
dc.typeArticleen_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.emailPhillips, DL: phillips@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ja0380648en_HK
dc.identifier.pmid14982460-
dc.identifier.scopuseid_2-s2.0-1542379884en_HK
dc.identifier.hkuros90772-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-1542379884&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume126en_HK
dc.identifier.issue8en_HK
dc.identifier.spage2501en_HK
dc.identifier.epage2514en_HK
dc.identifier.isiWOS:000189279700059-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridWong, CY=7404954160en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridChan, MCW=7402598116en_HK
dc.identifier.scopusauthoridLeung, KH=7401860609en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK

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