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*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

10 Citations (Scopus)

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 PPh3 affords an osmium(iv) phosphinidine complex [Os IV{N(H)PPh3}(L1)(OMe)](X) (X = PF 61a, ClO41b). If the reaction is carried out in CH 2Cl2 in the presence of excess pyrazine the osmium(iii) phosphinidine species [OsIII{N(H)PPh3}(L 1)(pz)](PF6) 2 can be generated. On the other hand, if the reaction is carried out in CH2Cl2 in the presence of a small amount of H2O, a μ-oxo osmium(iv) phosphinidine complex is obtained, [(L1){PPh3N(H)}OsIV-O-Os IV{N(H)PPh3}(L1)](PF6)23. Furthermore, if the reaction of [OsVI(N)(L1)(OH 2)]PF6 with PPh3 is done in the presence of 2, the μ-pyrazine species, [(L1){PPh3N(H)}Os III-pz-OsIII{N(H)PPh3}(L1)](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 [OsVI(N)(L1)(OH 2)](PF6) with PPh2-CC-PPh2 or PPh2-(CH2)3-PPh2 in MeOH affords the binuclear complexes [(MeO)(L1)OsIV{N(H)PPh 2-R-PPh2N(H)}OsIV(L1)(OMe)](PF 6)2 (R = CC 5, (CH2)36). Reaction of [OsVI(N)(L2)Cl] with PPh2FcPPh2 generates a novel trimetallic complex, [Cl(L2)Os IV{NPPh2-Fc-PPh2N}OsIV(L 2)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
Early online date26 Jan 2011
DOIs
Publication statusPublished - 7 Mar 2011

Scopus Subject Areas

  • Inorganic Chemistry

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