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Issue 14, 2011
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Dithiocarboxylate complexes of ruthenium(II) and osmium(II)

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Abstract

The ruthenium(II) complexes [Ru(R)(κ2-S2C·IPr)(CO)(PPh3)2]+ (R = CH[double bond, length as m-dash]CHBut, CH[double bond, length as m-dash]CHC6H4Me-4, C(C[triple bond, length as m-dash]CPh)[double bond, length as m-dash]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[triple bond, length as m-dash]CPh)[double bond, length as m-dash]CHPh)Cl(CO)(PPh3)2] in the presence of ammonium hexafluorophosphate. Similarly, the complexes [Ru(CH[double bond, length as m-dash]CHC6H4Me-4)(κ2-S2C·ICy)(CO)(PPh3)2]+ and [Ru(C(C[triple bond, length as m-dash]CPh)[double bond, length as m-dash]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[double bond, length as m-dash]CHBut, CH[double bond, length as m-dash]CHC6H4Me-4, C(C[triple bond, length as m-dash]CPh)[double bond, length as m-dash]CHPh). Two osmium analogues, [Os(CH[double bond, length as m-dash]CHC6H4Me-4)(κ2-S2C·IMes)(CO)(PPh3)2]+ and [Os(C(C[triple bond, length as m-dash]CPh)[double bond, length as m-dash]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[double bond, length as m-dash]CHC6H4Me-4)·IDip)Cl(CO)(PPh3)2]+, with a migrated vinyl group, is obtained. Over extended reaction times, [Ru(CH[double bond, length as m-dash]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[double bond, length as m-dash]CHC6H4Me-4)·IMes}Cl(CO)(PPh3)2]+via the intermediate [Ru(CH[double bond, length as m-dash]CHC6H4Me-4)(κ2-S2C·IMes)(CO)(PPh3)2]+. Structural studies are reported for [Ru(CH[double bond, length as m-dash]CHC6H4Me-4)(κ2-S2C·IPr)(CO)(PPh3)2]PF6 and [Ru(C(C[triple bond, length as m-dash]CPh)[double bond, length as m-dash]CHPh)(κ2-S2C·ICy)(CO)(PPh3)2]PF6.

Graphical abstract: Dithiocarboxylate complexes of ruthenium(ii) and osmium(ii)

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Publication details

The article was received on 11 Jan 2011, accepted on 31 Jan 2011 and first published on 04 Mar 2011


Article type: Paper
DOI: 10.1039/C1DT10048C
Citation: Dalton Trans., 2011,40, 3737-3747
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    Dithiocarboxylate complexes of ruthenium(II) and osmium(II)

    S. Naeem, A. L. Thompson, A. J. P. White, L. Delaude and J. D. E. T. Wilton-Ely, Dalton Trans., 2011, 40, 3737
    DOI: 10.1039/C1DT10048C

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