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Issue 17, 2012
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Diastereoselective synthesis and coordination chemistry of enantiopure keto-bis-(2-phosphametallocene)s

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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.

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

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Publication details

The article was received on 31 Aug 2011, accepted on 07 Dec 2011 and first published on 07 Mar 2012


Article type: Paper
DOI: 10.1039/C2DT11647B
Dalton Trans., 2012,41, 5155-5162

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

    D. Carmichael, X. F. le Goff, E. Muller, L. Ricard and M. Stankevič, Dalton Trans., 2012, 41, 5155
    DOI: 10.1039/C2DT11647B

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