Article: Binuclear (salen)osmium phosphinidine and phosphiniminato complexes

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TitleBinuclear (salen)osmium phosphinidine and phosphiniminato complexes
AuthorsChen, G2
Man, WL2
Yiu, SM2
Wong, TW2
Szeto, L1
Wong, WT1
Lau, TC2
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
CitationDalton Transactions, 2011, v. 40 n. 9, p. 1938-1944 [How to Cite?]
DOI: http://dx.doi.org/10.1039/c0dt01367f
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.
ISSN1477-9226
2011 Impact Factor: 3.838
2011 SCImago Journal Rankings: 0.254
DOIhttp://dx.doi.org/10.1039/c0dt01367f
ISI Accession Number IDWOS:000287378500015
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).

ReferencesReferences in Scopus
DC Field
Value
dc.contributor.authorChen, G
dc.contributor.authorMan, WL
dc.contributor.authorYiu, SM
dc.contributor.authorWong, TW
dc.contributor.authorSzeto, L
dc.contributor.authorWong, WT
dc.contributor.authorLau, TC
dc.date.accessioned2011-09-23T05:44:01Z
dc.date.available2011-09-23T05:44:01Z
dc.date.issued2011
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.
dc.description.natureLink_to_subscribed_fulltext
dc.identifier.citationDalton Transactions, 2011, v. 40 n. 9, p. 1938-1944 [How to Cite?]
DOI: http://dx.doi.org/10.1039/c0dt01367f
dc.identifier.doihttp://dx.doi.org/10.1039/c0dt01367f
dc.identifier.epage1944
dc.identifier.hkuros195810
dc.identifier.isiWOS:000287378500015
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).

dc.identifier.issn1477-9226
2011 Impact Factor: 3.838
2011 SCImago Journal Rankings: 0.254
dc.identifier.issue9
dc.identifier.pmid21267502
dc.identifier.scopuseid_2-s2.0-79951597940
dc.identifier.spage1938
dc.identifier.urihttp://hdl.handle.net/10722/139005
dc.identifier.volume40
dc.languageeng
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
dc.publisher.placeUnited Kingdom
dc.relation.ispartofDalton Transactions
dc.relation.referencesReferences in Scopus
dc.subjectBinuclear complexes
dc.subjectDiphosphine ligand
dc.subjectPhosphinidine
dc.subjectPyrazines
dc.subjectTrimetallic complexes
dc.titleBinuclear (salen)osmium phosphinidine and phosphiniminato complexes
dc.typeArticle
Author Affiliations
  1. The University of Hong Kong
  2. City University of Hong Kong