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Article: Binuclear (salen)osmium phosphinidine and phosphiniminato complexes

TitleBinuclear (salen)osmium phosphinidine and phosphiniminato complexes
Authors
KeywordsBinuclear complexes
Diphosphine ligand
Phosphinidine
Pyrazines
Trimetallic complexes
Issue Date2011
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
Citation
Dalton Transactions, 2011, v. 40 n. 9, p. 1938-1944 How to Cite?
Abstract
The preparation of a number of binuclear (salen)osmium phosphinidine and phosphiniminato complexes using various strategies are described. Treatment of [Os VI(N)(L 1)(sol)](X) (sol = H 2O or MeOH) with PPh 3 affords an osmium(iv) phosphinidine complex [Os IV{N(H)PPh 3}(L 1)(OMe)](X) (X = PF 61a, ClO 41b). If the reaction is carried out in CH 2Cl 2 in the presence of excess pyrazine the osmium(iii) phosphinidine species [Os III{N(H)PPh 3}(L 1)(pz)](PF 6) 2 can be generated. On the other hand, if the reaction is carried out in CH 2Cl 2 in the presence of a small amount of H 2O, a μ-oxo osmium(iv) phosphinidine complex is obtained, [(L 1){PPh 3N(H)}Os IV-O-Os IV{N(H)PPh 3}(L 1)](PF 6) 23. Furthermore, if the reaction of [Os VI(N)(L 1)(OH 2)]PF 6 with PPh 3 is done in the presence of 2, the μ-pyrazine species, [(L 1){PPh 3N(H)}Os III-pz-Os III{N(H)PPh 3}(L 1)](PF 6) 24 can be isolated. Novel binuclear osmium(iv) complexes can be prepared by the use of a diphosphine ligand to attack two Os VIN. Reaction of [Os VI(N)(L 1)(OH 2)](PF 6) with PPh 2-CC-PPh 2 or PPh 2-(CH 2) 3-PPh 2 in MeOH affords the binuclear complexes [(MeO)(L 1)Os IV{N(H)PPh 2-R-PPh 2N(H)}Os IV(L 1)(OMe)](PF 6) 2 (R = CC 5, (CH 2) 36). Reaction of [Os VI(N)(L 2)Cl] with PPh 2FcPPh 2 generates a novel trimetallic complex, [Cl(L 2)Os IV{NPPh 2-Fc-PPh 2N}Os IV(L 2)Cl] 7. The structures of 1b, 2, 3, 4, 5 and 7 have been determined by X-ray crystallography. © The Royal Society of Chemistry 2011.
Persistent Identifierhttp://hdl.handle.net/10722/139005
ISSN
2013 Impact Factor: 4.097
ISI Accession Number ID
Funding AgencyGrant Number
University Grants Committee, Hong KongAoE/P-03-08
Research Grants Council of Hong KongCityU 101607
Funding Information:

This work was supported by the Area of Excellence Scheme, University Grants Committee, Hong Kong (AoE/P-03-08) and the Research Grants Council of Hong Kong (CityU 101607).

References

 

DC FieldValueLanguage
dc.contributor.authorChen, Gen_HK
dc.contributor.authorMan, WLen_HK
dc.contributor.authorYiu, SMen_HK
dc.contributor.authorWong, TWen_HK
dc.contributor.authorSzeto, Len_HK
dc.contributor.authorWong, WTen_HK
dc.contributor.authorLau, TCen_HK
dc.date.accessioned2011-09-23T05:44:01Z-
dc.date.available2011-09-23T05:44:01Z-
dc.date.issued2011en_HK
dc.identifier.citationDalton Transactions, 2011, v. 40 n. 9, p. 1938-1944en_HK
dc.identifier.issn1477-9226en_HK
dc.identifier.urihttp://hdl.handle.net/10722/139005-
dc.description.abstractThe preparation of a number of binuclear (salen)osmium phosphinidine and phosphiniminato complexes using various strategies are described. Treatment of [Os VI(N)(L 1)(sol)](X) (sol = H 2O or MeOH) with PPh 3 affords an osmium(iv) phosphinidine complex [Os IV{N(H)PPh 3}(L 1)(OMe)](X) (X = PF 61a, ClO 41b). If the reaction is carried out in CH 2Cl 2 in the presence of excess pyrazine the osmium(iii) phosphinidine species [Os III{N(H)PPh 3}(L 1)(pz)](PF 6) 2 can be generated. On the other hand, if the reaction is carried out in CH 2Cl 2 in the presence of a small amount of H 2O, a μ-oxo osmium(iv) phosphinidine complex is obtained, [(L 1){PPh 3N(H)}Os IV-O-Os IV{N(H)PPh 3}(L 1)](PF 6) 23. Furthermore, if the reaction of [Os VI(N)(L 1)(OH 2)]PF 6 with PPh 3 is done in the presence of 2, the μ-pyrazine species, [(L 1){PPh 3N(H)}Os III-pz-Os III{N(H)PPh 3}(L 1)](PF 6) 24 can be isolated. Novel binuclear osmium(iv) complexes can be prepared by the use of a diphosphine ligand to attack two Os VIN. Reaction of [Os VI(N)(L 1)(OH 2)](PF 6) with PPh 2-CC-PPh 2 or PPh 2-(CH 2) 3-PPh 2 in MeOH affords the binuclear complexes [(MeO)(L 1)Os IV{N(H)PPh 2-R-PPh 2N(H)}Os IV(L 1)(OMe)](PF 6) 2 (R = CC 5, (CH 2) 36). Reaction of [Os VI(N)(L 2)Cl] with PPh 2FcPPh 2 generates a novel trimetallic complex, [Cl(L 2)Os IV{NPPh 2-Fc-PPh 2N}Os IV(L 2)Cl] 7. The structures of 1b, 2, 3, 4, 5 and 7 have been determined by X-ray crystallography. © The Royal Society of Chemistry 2011.en_HK
dc.languageengen_US
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/daltonen_HK
dc.relation.ispartofDalton Transactionsen_HK
dc.subjectBinuclear complexes-
dc.subjectDiphosphine ligand-
dc.subjectPhosphinidine-
dc.subjectPyrazines-
dc.subjectTrimetallic complexes-
dc.titleBinuclear (salen)osmium phosphinidine and phosphiniminato complexesen_HK
dc.typeArticleen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1039/c0dt01367fen_HK
dc.identifier.pmid21267502-
dc.identifier.scopuseid_2-s2.0-79951597940en_HK
dc.identifier.hkuros195810en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-79951597940&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume40en_HK
dc.identifier.issue9en_HK
dc.identifier.spage1938en_HK
dc.identifier.epage1944en_HK
dc.identifier.isiWOS:000287378500015-
dc.publisher.placeUnited Kingdomen_HK
dc.identifier.scopusauthoridChen, G=36664295500en_HK
dc.identifier.scopusauthoridMan, WL=7005307944en_HK
dc.identifier.scopusauthoridYiu, SM=43462142100en_HK
dc.identifier.scopusauthoridWong, TW=8043722600en_HK
dc.identifier.scopusauthoridSzeto, L=8398782100en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK
dc.identifier.scopusauthoridLau, TC=7102222310en_HK

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