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Article: Reactions of nitridorhenium(V) and -osmium(VI) complexes with acylating agents

TitleReactions of nitridorhenium(V) and -osmium(VI) complexes with acylating agents
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. 12, p. 3000-3005 How to Cite?
AbstractInteraction of Re(N)L2 [L = N(PSPh2)2] 1 with (CF3CO)2O or RCOCl afforded air-sensitive acylimido-Re(V) complexes trans-Re[NC(O)CF3](OCOCF3)L2 2 or trans-Re[NC(O)R]ClL2 (R = CCl2H 3, CClH2 4, CH3 5), respectively. Treatment of 1 with (CX3CO)2O followed by recrystallization from CH2Cl2/hexane in air led to the formation of the corresponding parent imido complexes trans-Re(NH)(OCOCX3)L2 (X = F 6, Cl 7). The structure of 7 has been characterized by X-ray crystallography. The Re−N, average Re−S, and Re−O distances are 1.664(3), 2.441, and 2.116(3) Å, respectively. Deprotonation of 6 or 7 with Et3N gave 1. Recrystallization of 3 from CH2Cl2/hexane in air resulted in oxo-imido exchange and the isolation of the oxo-Re(V) species trans-Re(O)ClL2. Treatment of 1 with tosyl anhydride gave trans-Re(NH)(OTs)L2 (OTs = tosyl) 8. Reaction of [n-Bu4N][OsNCl4] with KL afforded trans-Os(N)ClL2 9, which has been characterized by X-ray crystallography. The Os−N, Os−Cl, and average Os−S bond distances in 9 are 1.64(1), 2.577(4), and 2.429 Å, respectively. Treatment of 10 with (CF3CO)2O, Ag(CF3CO2), or CF3CO2H resulted in chloride substitution and the formation of trans-Os(N)(OCOCF3)L2 10. The Os−N, Os−O, and average Os−S distances in 10 are 1.643(5), 2.271(4), and 2.419 Å, respectively. Treatment of 1 with [Ph3C]BF4 resulted in the isolation of trans-Re(NCPh3)(F)L2 11, presumably via the cationic tritylimido intermediate [Re(NCPh3)L2]+. Reaction of 9 with [Ph3C]BF4 led to chloride abstraction and the formation of five-coordinate [Os(N)L2]BF4 12. The Os−N and average Os−S distances in 12 are 1.646(5) and 2.364 Å, respectively.
Persistent Identifierhttp://hdl.handle.net/10722/70251
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorLeung, WHen_HK
dc.contributor.authorChim, JLCen_HK
dc.contributor.authorWilliams, IDen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:21:08Z-
dc.date.available2010-09-06T06:21:08Z-
dc.date.issued1999en_HK
dc.identifier.citationInorganic Chemistry, 1999, v. 38 n. 12, p. 3000-3005en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70251-
dc.description.abstractInteraction of Re(N)L2 [L = N(PSPh2)2] 1 with (CF3CO)2O or RCOCl afforded air-sensitive acylimido-Re(V) complexes trans-Re[NC(O)CF3](OCOCF3)L2 2 or trans-Re[NC(O)R]ClL2 (R = CCl2H 3, CClH2 4, CH3 5), respectively. Treatment of 1 with (CX3CO)2O followed by recrystallization from CH2Cl2/hexane in air led to the formation of the corresponding parent imido complexes trans-Re(NH)(OCOCX3)L2 (X = F 6, Cl 7). The structure of 7 has been characterized by X-ray crystallography. The Re−N, average Re−S, and Re−O distances are 1.664(3), 2.441, and 2.116(3) Å, respectively. Deprotonation of 6 or 7 with Et3N gave 1. Recrystallization of 3 from CH2Cl2/hexane in air resulted in oxo-imido exchange and the isolation of the oxo-Re(V) species trans-Re(O)ClL2. Treatment of 1 with tosyl anhydride gave trans-Re(NH)(OTs)L2 (OTs = tosyl) 8. Reaction of [n-Bu4N][OsNCl4] with KL afforded trans-Os(N)ClL2 9, which has been characterized by X-ray crystallography. The Os−N, Os−Cl, and average Os−S bond distances in 9 are 1.64(1), 2.577(4), and 2.429 Å, respectively. Treatment of 10 with (CF3CO)2O, Ag(CF3CO2), or CF3CO2H resulted in chloride substitution and the formation of trans-Os(N)(OCOCF3)L2 10. The Os−N, Os−O, and average Os−S distances in 10 are 1.643(5), 2.271(4), and 2.419 Å, respectively. Treatment of 1 with [Ph3C]BF4 resulted in the isolation of trans-Re(NCPh3)(F)L2 11, presumably via the cationic tritylimido intermediate [Re(NCPh3)L2]+. Reaction of 9 with [Ph3C]BF4 led to chloride abstraction and the formation of five-coordinate [Os(N)L2]BF4 12. The Os−N and average Os−S distances in 12 are 1.646(5) and 2.364 Å, respectively.-
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.titleReactions of nitridorhenium(V) and -osmium(VI) complexes with acylating agentsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1669&volume=38&spage=3000&epage=3005&date=1999&atitle=Reactions+of+nitridorhenium(V)+and+-osmium(VI)+complexes+with+acylating+agentsen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.identifier.doi10.1021/ic981244b-
dc.identifier.hkuros45548en_HK
dc.identifier.issue12-
dc.identifier.isiWOS:000080959800035-

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