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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
2013 Impact Factor: 4.097
 
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 FieldValue
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
2013 Impact Factor: 4.097
 
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
 
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<contributor.author>Yiu, SM</contributor.author>
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<contributor.author>Szeto, L</contributor.author>
<contributor.author>Wong, WT</contributor.author>
<contributor.author>Lau, TC</contributor.author>
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<description.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 &#956;-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 &#956;-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. &#169; The Royal Society of Chemistry 2011.</description.abstract>
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Author Affiliations
  1. The University of Hong Kong
  2. City University of Hong Kong