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Article: Probing ruthenium-acetylide bonding interactions: Synthesis, electrochemistry, and spectroscopic studies of acetylide-ruthenium complexes supported by tetradentate macrocyclic amine and diphosphine ligands

TitleProbing ruthenium-acetylide bonding interactions: Synthesis, electrochemistry, and spectroscopic studies of acetylide-ruthenium complexes supported by tetradentate macrocyclic amine and diphosphine ligands
Authors
Issue Date2005
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, 2005, v. 127 n. 40, p. 13997-14007 How to Cite?
AbstractThe synthesis and spectroscopic properties of trans-[RuL 4(C≡CAr)2] (L4 = two 1,2-bis- (dimethylphosphino)ethane, (dmpe)2; 1,5,9,13-tetramethyl-1,5,9,13- tetraazacyclohexadecane, 16-TMC; 1,-12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8- dioxacyclopentadecane, N2O2) are described. Investigations into the effects of varying the [RuL4] core, acetylide ligands, and acetylide chain length for the [-C≡C(C6H 4C=C)n-1Ph] and [-C≡C(C6H 4)n-1Ph] (n = 1-3) series upon the electronic and electrochemical characteristics of trans-[RuL4(C≡CAr) 2]0/+ are presented. DFT and TD-DFT calculations have been performed on frans-[Ru(L′)4(C≡CAr)2] 0/+ (L′ = PH3 and NH3) to examine the metal-acetylide π-interaction and the nature of the associated electronic transition(s). It was observed that (1) the relationship between the transition energy and 1/n for trans-[Ru(dmpe)2{C≡C(C6H 4C≡C)n-1Ph}2] (n = 1-3) is linear, and (2) the sum of the dπRuII) → π*(C≡CAr) MLCT energy for trans-[Ru(16-TMC or N2O2)(C≡CAr) 2] and the π-(C≡CAr) → dπ(RuIII) LMCT energy for trans-[Ru(16-TMC or N2O2)(C≡CAr) 2]+ corresponds to the intraligand ππ* absorption energy for trans-[Ru(16-TMC or N2O2) (C≡CAr)2]. The crystal structure of trans-[Ru(dmpe) 2-{C≡C(C6H4C≡C)2Ph} 2] shows that the two edges of the molecule are separated by 41.7 Å. The electrochemical and spectroscopic properties of these complexes can be systematically tuned by modifying L4 and Ar to give E 1/2 values for oxidation of trans-[RuL4(C≡CAr) 2] that span over 870 mV and λmax values of trans-[RuL4(C≡CAr)2] that range from 19 230 to 31 750 cm-1. The overall experimental findings suggest that the π-back-bonding interaction in trans-[RuL4(C≡CAr) 2] is weak and the [RuL4] moiety in these molecules may be considered to be playing a "dopant" role in a linear rigid π-conjugated rod. © 2005 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/69881
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.authorHan, Jen_HK
dc.contributor.authorLeung, KHen_HK
dc.contributor.authorPhillips, DLen_HK
dc.contributor.authorWong, KYen_HK
dc.contributor.authorZhu, Nen_HK
dc.date.accessioned2010-09-06T06:17:41Z-
dc.date.available2010-09-06T06:17:41Z-
dc.date.issued2005en_HK
dc.identifier.citationJournal Of The American Chemical Society, 2005, v. 127 n. 40, p. 13997-14007en_HK
dc.identifier.issn0002-7863en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69881-
dc.description.abstractThe synthesis and spectroscopic properties of trans-[RuL 4(C≡CAr)2] (L4 = two 1,2-bis- (dimethylphosphino)ethane, (dmpe)2; 1,5,9,13-tetramethyl-1,5,9,13- tetraazacyclohexadecane, 16-TMC; 1,-12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8- dioxacyclopentadecane, N2O2) are described. Investigations into the effects of varying the [RuL4] core, acetylide ligands, and acetylide chain length for the [-C≡C(C6H 4C=C)n-1Ph] and [-C≡C(C6H 4)n-1Ph] (n = 1-3) series upon the electronic and electrochemical characteristics of trans-[RuL4(C≡CAr) 2]0/+ are presented. DFT and TD-DFT calculations have been performed on frans-[Ru(L′)4(C≡CAr)2] 0/+ (L′ = PH3 and NH3) to examine the metal-acetylide π-interaction and the nature of the associated electronic transition(s). It was observed that (1) the relationship between the transition energy and 1/n for trans-[Ru(dmpe)2{C≡C(C6H 4C≡C)n-1Ph}2] (n = 1-3) is linear, and (2) the sum of the dπRuII) → π*(C≡CAr) MLCT energy for trans-[Ru(16-TMC or N2O2)(C≡CAr) 2] and the π-(C≡CAr) → dπ(RuIII) LMCT energy for trans-[Ru(16-TMC or N2O2)(C≡CAr) 2]+ corresponds to the intraligand ππ* absorption energy for trans-[Ru(16-TMC or N2O2) (C≡CAr)2]. The crystal structure of trans-[Ru(dmpe) 2-{C≡C(C6H4C≡C)2Ph} 2] shows that the two edges of the molecule are separated by 41.7 Å. The electrochemical and spectroscopic properties of these complexes can be systematically tuned by modifying L4 and Ar to give E 1/2 values for oxidation of trans-[RuL4(C≡CAr) 2] that span over 870 mV and λmax values of trans-[RuL4(C≡CAr)2] that range from 19 230 to 31 750 cm-1. The overall experimental findings suggest that the π-back-bonding interaction in trans-[RuL4(C≡CAr) 2] is weak and the [RuL4] moiety in these molecules may be considered to be playing a "dopant" role in a linear rigid π-conjugated rod. © 2005 American Chemical Society.en_HK
dc.languageengen_HK
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 ruthenium-acetylide bonding interactions: Synthesis, electrochemistry, and spectroscopic studies of acetylide-ruthenium complexes supported by tetradentate macrocyclic amine and diphosphine ligandsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0002-7863&volume=127&spage=13997&epage=14007&date=2005&atitle=Probing+Ruthenium?Acetylide+Bonding+Interactions:++Synthesis,+Electrochemistry,+and+Spectroscopic+Studies+of+Acetylide?Ruthenium+Complexes+Supported+by+Tetradentate+Macrocyclic+Amine+and+Diphosphine+Ligands+en_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_fulltext-
dc.identifier.doi10.1021/ja053076+en_HK
dc.identifier.pmid16201822-
dc.identifier.scopuseid_2-s2.0-26644453706en_HK
dc.identifier.hkuros157103en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-26644453706&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume127en_HK
dc.identifier.issue40en_HK
dc.identifier.spage13997en_HK
dc.identifier.epage14007en_HK
dc.identifier.isiWOS:000232413300056-
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.scopusauthoridHan, J=26643236400en_HK
dc.identifier.scopusauthoridLeung, KH=7401860609en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK
dc.identifier.scopusauthoridWong, KY=7404760030en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK

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