Synthesis and reactivity of dialkyldithiophosphate complexes of ruthenium(ii)†
Abstract
The ruthenium(II) complexes [Ru(CH![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
CHR){κ2-S2P(OEt)2}(CO)(PPh3)2] (R = But, C6H4Me-4) are formed on reaction of (NH4)[S2P(OEt)2] with [Ru(CHCHR)Cl(CO)(BTD)(PPh3)2] (BTD = ![[triple bond, length as m-dash]](https://www.rsc.org/images/entities/char_e002.gif)
CPh)CHPh)Cl(CO)(PPh3)2] loses a C–CCHPh){κ2-S2P(OEt)2}(CO)(PPh3)]. The stilbenyl complexes [Ru(CPhCHPh)Cl(CA)(PPh3)2] (A = O, S) react with (NH4)[S2P(OEt)2] to provide the dimers [Ru(CPhCHPh){μ–κ1–κ2–S2P(OEt)2}(CA)(PPh3)]2. Treatment of the CHPh){κ2-S2P(OEt)2}(CO)(PPh3)]. On treatment with excess CHC6H4Me-4){κ2-S2P(OEt)2}(CO)(PPh3)2]. The compounds [Ru(CHCHR){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 HCCR. On stirring [RuH{κ2-S2P(OEt)2}(CO)(PPh3)2] over a longer period of time with excess CC6H4Me–4){κ2-S2P(OEt)2}(CO)(PPh3)2] is generated. Heating [Ru(CHCHC6H4Me-4){κ2-S2P(OEt)2}(CO)(PPh3)2] with excess 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 CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] to yield [Ru(CHCHC6H4Me-4){κ2-OP(S)(OEt)2}(CO)(PPh3)2]. The molecular structure of [Ru(CHCHCPh2OH){κ2-S2P(OEt)2}(CO)(PPh3)2] was determined crystallographically.
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