Diastereoselective synthesis and coordination chemistry of enantiopure keto-bis-(2-phosphametallocene)s

Abstract : Enantiopure 2-(chlorocarbonyl)phosphametallocenes [MCp*(2-{COCl}-3,4-Me2-5-Ph-PC4)] (M = Fe, Ru) react with phospholide anions to give 2-phosphametallocene-2′-acylphospholides K[MCp*(2-CO-2′-{3′,4′-Me2-5′-PhPC4}-3,4-Me2-5-Ph-PC4)] (M = Fe, Ru) and these have been converted into keto-bis-(2-phosphametallocene)s through reaction with [FeClCp*(tmeda)]; templation of this process with CuBr gives rise to the C2- (or pseudo-C2- when M = Ru) symmetric form of [{MCp*(3,4-Me2-5-Ph-PC4)}2-2,2′-(CO)] (M = Fe, Ru; Fe, Fe) with high (>95%) diastereoselectivity. X-Ray structures of these ligands coordinated to [RuCp*Cl] and [PtCl2] centres show that the spatial orientation of the very flexible keto-bis-(2-phosphametallocene) structure is highly responsive to the coordination sphere of the chelated platinum or ruthenium centre.
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Submitted on : Friday, November 15, 2013 - 4:33:52 PM
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Duncan Carmichael, X. Le Goff, Eric Muller, Louis Ricard, Marek Stankevic. Diastereoselective synthesis and coordination chemistry of enantiopure keto-bis-(2-phosphametallocene)s. Dalton Transactions, Royal Society of Chemistry, 2012, 41, pp.5155-5162. ⟨10.1039/C2DT11647B⟩. ⟨hal-00904996⟩

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