"Dithiocarboxylate Complexes of Ruthenium(II) and Osmium(II)"

Saira Naeem, Amber L. Thompson, Andrew J. P. White, Lionel Delaude, and James D. E. T. Wilton-Ely

Journal Cover 
          source: Dalton Transactions
            year: 2011
          volume: 40
      first page: 3737
       last page: 3747
             doi: 10.1039/c1dt10048c
graphical abstract

Abstract: The ruthenium(II) complexes [Ru(R)(κ2-S2C·IPr)(CO)(PPh3)2]+ (R = CH=CHBut, CH=CHC6H4Me-4, C(C≡CPh)=CHPh) are formed on reaction of IPr·CS2 with [Ru(R)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole) or [Ru(C(C≡CPh)=CHPh)Cl(CO)(PPh3)2] in the presence of ammonium hexafluorophosphate. Similarly, the complexes [Ru(CH=CHC6H4Me-4)(κ2-S2C·ICy)(CO)(PPh3)2]+ and [Ru(C(C≡CPh)=CHPh)(κ2-S2C·ICy)(CO)(PPh3)2]+ are formed in the same manner when ICy·CS2 is employed. The ligand IMes·CS2 reacts with [Ru(R)Cl(CO)(BTD)(PPh3)2] to form the compounds [Ru(R)(κ2-S2C·IMes)(CO)(PPh3)2]+ (R = CH=CHBut, CH=CHC6H4Me-4, C(C≡CPh)=CHPh). Two osmium analogues, [Os(CH=CHC6H4Me-4)(κ2-S2C·IMes)(CO)(PPh3)2]+ and [Os(C(C≡CPh)=CHPh)(κ2-S2C·IMes)(CO)(PPh3)2]+ were also prepared. When the more bulky diisopropylphenyl derivative IDip·CS2 is used, an unusual product, [Ru(κ2-SC(H)S(CH=CHC6H4Me-4)·IDip)Cl(CO)(PPh3)2]+, with a migrated vinyl group, is obtained. Over extended reaction times, [Ru(CH=CHC6H4Me-4)Cl(BTD)(CO)(PPh3)2] also reacts with IMes·CS2 and NH4PF6 to yield the analogous product [Ru(κ2-SC(H)S(CH=CHC6H4Me- 4)·IMes)Cl(CO)(PPh3)2]+ via the intermediate [Ru(CH=CHC6H4Me-4)(κ2- S2C·IMes)(CO)(PPh3)2]+. Structural studies are reported for [Ru(CH=CHC6H4Me-4)(κ2-S2C·IPr)(CO)(PPh3)2]PF6 and [Ru(C(C≡CPh)=CHPh)(κ2-S2C·ICy)(CO)(PPh3)2]PF6.

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