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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
Title | 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 |
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Authors | |
Issue Date | 2004 |
Publisher | American 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? |
Abstract | The 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 Identifier | http://hdl.handle.net/10722/167899 |
ISSN | 2023 Impact Factor: 14.4 2023 SCImago Journal Rankings: 5.489 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
---|---|---|
dc.contributor.author | Wong, CY | en_HK |
dc.contributor.author | Che, CM | en_HK |
dc.contributor.author | Chan, MCW | en_HK |
dc.contributor.author | Leung, KH | en_HK |
dc.contributor.author | Phillips, DL | en_HK |
dc.contributor.author | Zhu, N | en_HK |
dc.date.accessioned | 2012-10-08T03:12:41Z | - |
dc.date.available | 2012-10-08T03:12:41Z | - |
dc.date.issued | 2004 | en_HK |
dc.identifier.citation | Journal Of The American Chemical Society, 2004, v. 126 n. 8, p. 2501-2514 | en_HK |
dc.identifier.issn | 0002-7863 | en_HK |
dc.identifier.uri | http://hdl.handle.net/10722/167899 | - |
dc.description.abstract | The 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.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html | en_HK |
dc.relation.ispartof | Journal of the American Chemical Society | en_HK |
dc.title | 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 | en_HK |
dc.type | Article | en_HK |
dc.identifier.email | Che, CM: cmche@hku.hk | en_HK |
dc.identifier.email | Phillips, DL: phillips@hku.hk | en_HK |
dc.identifier.email | Zhu, N: nzhu@hkucc.hku.hk | en_HK |
dc.identifier.authority | Che, CM=rp00670 | en_HK |
dc.identifier.authority | Phillips, DL=rp00770 | en_HK |
dc.identifier.authority | Zhu, N=rp00845 | en_HK |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/ja0380648 | en_HK |
dc.identifier.pmid | 14982460 | - |
dc.identifier.scopus | eid_2-s2.0-1542379884 | en_HK |
dc.identifier.hkuros | 90772 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-1542379884&selection=ref&src=s&origin=recordpage | en_HK |
dc.identifier.volume | 126 | en_HK |
dc.identifier.issue | 8 | en_HK |
dc.identifier.spage | 2501 | en_HK |
dc.identifier.epage | 2514 | en_HK |
dc.identifier.isi | WOS:000189279700059 | - |
dc.publisher.place | United States | en_HK |
dc.identifier.scopusauthorid | Wong, CY=7404954160 | en_HK |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_HK |
dc.identifier.scopusauthorid | Chan, MCW=7402598116 | en_HK |
dc.identifier.scopusauthorid | Leung, KH=7401860609 | en_HK |
dc.identifier.scopusauthorid | Phillips, DL=7404519365 | en_HK |
dc.identifier.scopusauthorid | Zhu, N=7201449530 | en_HK |
dc.identifier.issnl | 0002-7863 | - |