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Synthesis and reactivity of dialkyldithiophosphate complexes of ruthenium(ii)†
Payel Patel,Saira Naeem,Andrew J. P. White,James D. E. T. Wilton-Ely
RSC Advances Pub Date : 12/02/2011 00:00:00 , DOI:10.1039/C1RA00973G
Abstract

The ruthenium(II) complexes [Ru(CH[double bond, length as m-dash]CHR){κ2-S2P(OEt)2}(CO)(PPh3)2] (R = But, C6H4Me-4) are formed on reaction of (NH4)[S2P(OEt)2] with [Ru(CH[double bond, length as m-dash]CHR)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole), while the enynyl complex [Ru(C(C[triple bond, length as m-dash]CPh)[double bond, length as m-dash]CHPh)Cl(CO)(PPh3)2] loses a phosphine on treatment with the same ligand to yield [Ru(η3-PhC[triple bond, length as m-dash]C–C[double bond, length as m-dash]CHPh){κ2-S2P(OEt)2}(CO)(PPh3)]. The stilbenyl complexes [Ru(CPh[double bond, length as m-dash]CHPh)Cl(CA)(PPh3)2] (A = O, S) react with (NH4)[S2P(OEt)2] to provide the dimers [Ru(CPh[double bond, length as m-dash]CHPh){μ–κ1κ2–S2P(OEt)2}(CA)(PPh3)]2. Treatment of the thiocarbonyl complex with carbon monoxide results in migratory insertion of the vinyl and CS ligands to provide [Ru(η2-SCCPh[double bond, length as m-dash]CHPh){κ2-S2P(OEt)2}(CO)(PPh3)]. On treatment with excess 4-ethynyltoluene, the known compound [RuH{κ2-S2P(OEt)2}(CO)(PPh3)2] undergoes insertion of the alkyne to provide an alternative route to [Ru(CH[double bond, length as m-dash]CHC6H4Me-4){κ2-S2P(OEt)2}(CO)(PPh3)2]. The compounds [Ru(CH[double bond, length as m-dash]CHR){κ2-S2P(OEt)2}(CO)(PPh3)2] (R = n-C4H9, CH2OSi(But)Me2, CO2Me, Fc, CPh2OH, (HO)C6H10) were prepared cleanly by this route using HC[triple bond, length as m-dash]CR. On stirring [RuH{κ2-S2P(OEt)2}(CO)(PPh3)2] over a longer period of time with excess 4-ethynyltoluene, the acetylide [Ru(C[triple bond, length as m-dash]CC6H4Me–4){κ2-S2P(OEt)2}(CO)(PPh3)2] is generated. Heating [Ru(CH[double bond, length as m-dash]CHC6H4Me-4){κ2-S2P(OEt)2}(CO)(PPh3)2] with excess 3,3-dimethylbut-1-yne in 1,2-dichloroethane led to elimination of the vinyl ligand and formation of the acetylide compound [Ru(C[triple bond, length as m-dash]CBut){κ2-S2P(OEt)2}(CO)(PPh3)2]. A small amount of the side product, [RuCl{κ2-S2P(OEt)2}(CO)(PPh3)2], was also formed. This could be obtained directly from the reaction of [RuH{κ2-S2P(OEt)2}(CO)(PPh3)2] with N-chlorosuccinimide. The related mixed-donor ligand, K[OP(S)(OEt)2], reacts with [Ru(CH[double bond, length as m-dash]CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] to yield [Ru(CH[double bond, length as m-dash]CHC6H4Me-4){κ2-OP(S)(OEt)2}(CO)(PPh3)2]. The molecular structure of [Ru(CH[double bond, length as m-dash]CHCPh2OH){κ2-S2P(OEt)2}(CO)(PPh3)2] was determined crystallographically.

Graphical abstract: Synthesis and reactivity of dialkyldithiophosphate complexes of ruthenium(ii)
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