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Article: Synthesis and electrochemistry of ruthenium complexes with an oxygen tripod ligand

TitleSynthesis and electrochemistry of ruthenium complexes with an oxygen tripod ligand
Authors
Issue Date1999
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 1999, v. 38 n. 1, p. 136-143 How to Cite?
AbstractReaction of [Ru(COD)Cl2]x (COD = 1,5-cyclooctadiene) with NaLOEt afforded LOEt(COD)RuCl (1). The average Ru-O, average Ru-C and Ru-Cl distances in 1 are 2.129, 2.164, and 2.398(3) ̊, respectively. Treatment of 1 with AgBF4 in acetone/H2O afforded [LOEt(COD)Ru(OH2)]BF4 (2), which reacts with L to give the respective adducts [LOEt(COD)RuL]BF4 (L = t-BuNH2 (3), p-MeC6H4NH2 (4), NH3 (5), N2H4, (6), pyridine (7), 4,4′-bipyridine (8), MeCN (9), Et2S (10), and Me2SO (11)). The structures of 3 and 4 have been characterized by X-ray crystallography. The average Ru-O, Ru-C, and Ru-N distances in 3 are 2.115, 2.162, and 2.197(6) ̊, respectively. The corresponding bond distances for 4 are 2.113, 2.160 and 2.174(5) A. Reaction of 8 with 2 afforded the 4,4′-bipyridine-bridged binuclear complex [{LOEt(COD)Ru}2(μ-4,4′-bipy)](PF6)2 (12). Deprotonation of complexes 2 and 4 gave the hydroxide LOEt(COD)RuOH (13) and the amide LOEt(COD)Ru(NHC6H4Me-p) (14), respectively. The structure of [LOEt(CO)(PPh3)Ru(OH2)]BF4 (15) has been characterized by X-ray crystallography. The average Ru-O(LOEt), Ru-C, Ru-P, and Ru-O(aquo) distances in 15 are 2.118, 1.83(1), 2.285(3), and 2.091(7) A, respectively. Interaction of 15 with p-MeC6H4NH2 PPh3, and NaN3 gave [LOEt(CO)(PPh3)Ru(p-MeC6H4NH 2)]BF4 (16), [LOEt(PPh3)2Ru(CO)]PF6 (17), and LOEt(CO)(PPh3)RuN3 (18), respectively. Deprotonation of 15 and 16 afforded the hydroxide LOEt(CO)(PPh3)Ru(OH) (19) and amide LOEt(CO)(PPh3)Ru(NHC6H4Me-p) (20), respectively. Treatment of Ru(CO)Cl(H)(PPh3)3 with NaLOEt afforded the hydride LOEt(CO)(PPh3)RuH (21), which reacts with tosyl azide to give the Ru(II) tosylamide LOEt(CO)(PPh3)Ru(NHSO2C6H 4Me-p) (22). Reaction of [LOEt(PPh3)2Ru(MeOH)]+ with t-BuNC, CNpy (4-cyanopyridine), Me2SO, and SO2 afforded the respective adducts [LOEt(PPh3)2RuL]+ (L = t-BuNC (23), CNpy (24), Me2SO (25), SO2 (26)), isolated as their PF6 salts. The cyclic voltammograms for the Ru-LOEt complexes show reversible oxidation couples assignable to Ru(III/II) couples. The availability of electrons in the LOEtRu complexes for back-bonding can be accessed by their v(C≡O) and Ru(III/II) potentials. © 1999 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/69533
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLeung, WHen_HK
dc.contributor.authorChan, EYYen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:14:32Z-
dc.date.available2010-09-06T06:14:32Z-
dc.date.issued1999en_HK
dc.identifier.citationInorganic Chemistry, 1999, v. 38 n. 1, p. 136-143en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69533-
dc.description.abstractReaction of [Ru(COD)Cl2]x (COD = 1,5-cyclooctadiene) with NaLOEt afforded LOEt(COD)RuCl (1). The average Ru-O, average Ru-C and Ru-Cl distances in 1 are 2.129, 2.164, and 2.398(3) ̊, respectively. Treatment of 1 with AgBF4 in acetone/H2O afforded [LOEt(COD)Ru(OH2)]BF4 (2), which reacts with L to give the respective adducts [LOEt(COD)RuL]BF4 (L = t-BuNH2 (3), p-MeC6H4NH2 (4), NH3 (5), N2H4, (6), pyridine (7), 4,4′-bipyridine (8), MeCN (9), Et2S (10), and Me2SO (11)). The structures of 3 and 4 have been characterized by X-ray crystallography. The average Ru-O, Ru-C, and Ru-N distances in 3 are 2.115, 2.162, and 2.197(6) ̊, respectively. The corresponding bond distances for 4 are 2.113, 2.160 and 2.174(5) A. Reaction of 8 with 2 afforded the 4,4′-bipyridine-bridged binuclear complex [{LOEt(COD)Ru}2(μ-4,4′-bipy)](PF6)2 (12). Deprotonation of complexes 2 and 4 gave the hydroxide LOEt(COD)RuOH (13) and the amide LOEt(COD)Ru(NHC6H4Me-p) (14), respectively. The structure of [LOEt(CO)(PPh3)Ru(OH2)]BF4 (15) has been characterized by X-ray crystallography. The average Ru-O(LOEt), Ru-C, Ru-P, and Ru-O(aquo) distances in 15 are 2.118, 1.83(1), 2.285(3), and 2.091(7) A, respectively. Interaction of 15 with p-MeC6H4NH2 PPh3, and NaN3 gave [LOEt(CO)(PPh3)Ru(p-MeC6H4NH 2)]BF4 (16), [LOEt(PPh3)2Ru(CO)]PF6 (17), and LOEt(CO)(PPh3)RuN3 (18), respectively. Deprotonation of 15 and 16 afforded the hydroxide LOEt(CO)(PPh3)Ru(OH) (19) and amide LOEt(CO)(PPh3)Ru(NHC6H4Me-p) (20), respectively. Treatment of Ru(CO)Cl(H)(PPh3)3 with NaLOEt afforded the hydride LOEt(CO)(PPh3)RuH (21), which reacts with tosyl azide to give the Ru(II) tosylamide LOEt(CO)(PPh3)Ru(NHSO2C6H 4Me-p) (22). Reaction of [LOEt(PPh3)2Ru(MeOH)]+ with t-BuNC, CNpy (4-cyanopyridine), Me2SO, and SO2 afforded the respective adducts [LOEt(PPh3)2RuL]+ (L = t-BuNC (23), CNpy (24), Me2SO (25), SO2 (26)), isolated as their PF6 salts. The cyclic voltammograms for the Ru-LOEt complexes show reversible oxidation couples assignable to Ru(III/II) couples. The availability of electrons in the LOEtRu complexes for back-bonding can be accessed by their v(C≡O) and Ru(III/II) potentials. © 1999 American Chemical Society.en_HK
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_HK
dc.relation.ispartofInorganic Chemistryen_HK
dc.titleSynthesis and electrochemistry of ruthenium complexes with an oxygen tripod liganden_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1669&volume=38&spage=136&epage=143&date=1999&atitle=Synthesis+and+electrochemistry+of+ruthenium+complexes+with+an+oxygen+tripod+liganden_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ic980196s-
dc.identifier.scopuseid_2-s2.0-0000914402en_HK
dc.identifier.hkuros45563en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0000914402&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume38en_HK
dc.identifier.issue1en_HK
dc.identifier.spage136en_HK
dc.identifier.epage143en_HK
dc.identifier.isiWOS:000078066900020-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridLeung, WH=7201504510en_HK
dc.identifier.scopusauthoridChan, EYY=7401994108en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK

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