Binuclear (salen)osmium phosphinidine and phosphiniminato complexes

Gui Chen, Wai Lun Man, Shek Man Yiu, Tsz Wing Wong, Lap Szeto, Wing Tak Wong, Tai Chu Lau

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Abstract

The preparation of a number of binuclear (salen)osmium phosphinidine and phosphiniminato complexes using various strategies are described. Treatment of [OsVI(N)(L1)(sol)](X) (sol = H2O or MeOH) with PPh3affords an osmium(iv) phosphinidine complex [OsIV{N(H)PPh3}(L1)(OMe)](X) (X = PF61a, ClO41b). If the reaction is carried out in CH2Cl2in the presence of excess pyrazine the osmium(iii) phosphinidine species [OsIII{N(H)PPh3}(L1)(pz)](PF6) 2 can be generated. On the other hand, if the reaction is carried out in CH2Cl2in the presence of a small amount of H2O, a μ-oxo osmium(iv) phosphinidine complex is obtained, [(L1){PPh3N(H)}OsIV-O-OsIV{N(H)PPh3}(L1)](PF6)23. Furthermore, if the reaction of [OsVI(N)(L1)(OH2)]PF6with PPh3is done in the presence of 2, the μ-pyrazine species, [(L1){PPh3N(H)}OsIII-pz-OsIII{N(H)PPh3}(L1)](PF6)24 can be isolated. Novel binuclear osmium(iv) complexes can be prepared by the use of a diphosphine ligand to attack two OsVIN. Reaction of [OsVI(N)(L1)(OH2)](PF6) with PPh2-CC-PPh2or PPh2-(CH2)3-PPh2in MeOH affords the binuclear complexes [(MeO)(L1)OsIV{N(H)PPh2-R-PPh2N(H)}OsIV(L1)(OMe)](PF6)2(R = CC 5, (CH2)36). Reaction of [OsVI(N)(L2)Cl] with PPh2FcPPh2generates a novel trimetallic complex, [Cl(L2)OsIV{NPPh2-Fc-PPh2N}OsIV(L2)Cl] 7. The structures of 1b, 2, 3, 4, 5 and 7 have been determined by X-ray crystallography.
Original languageEnglish
Pages (from-to)1938-1944
Number of pages7
JournalDalton Transactions
Volume40
Issue number9
DOIs
Publication statusPublished - 7 Mar 2011
Externally publishedYes

ASJC Scopus subject areas

  • Inorganic Chemistry

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