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Issue 4, 2016

Stabilisation of carbonyl free amidinato-manganese(ii) hydride complexes: “masked” sources of manganese(i) in organometallic synthesis

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Abstract

Reaction of the amidinato-manganese(II) bromide complex, [{(κ2-N,N′-Piso)Mn(μ-Br)}3(THF)2] (Piso = [(DipN)2CBut], Dip = 2,6-diisopropylphenyl), with K[BHEt3] affords the first example of a structurally authenticated amidinato-manganese(II) hydride complex, [{(N-,η3-arene-Piso)Mn(μ-H)2}2], via a process which involves a change in the amidinate coordination mode. Treatment of the bulkier precursor complex, [{(Piso′′)Mn(μ-Br)}n] (Piso′′ = [(Dip′′N)2CBut], Dip′′ = C6H2Pri2(CPh3)-2,6,4), with K[BHEt3] did not lead to an isolable manganese hydride complex, but its reaction with the magnesium(I) complex, [{(MesNacnac)Mg}2] (MesNacnac = [(MesNCMe)2CH], Mes = mesityl), did. This reaction presumably proceeds via a reactive manganese(I) intermediate, which abstracts hydrogen from a reaction component to give [{(κ2-N,N′-Piso′′)Mn(μ-H)}3]. A comparison of the reactivities of [{(N-,η3-arene-Piso)Mn(μ-H)2}2] and the isomorphous manganese(I) complex, [{(N-,η3-arene-Piso)Mn}2], toward CO, O2 and N2O was carried out. Reactions with the manganese(I) and manganese(II) species gave identical results, namely the formation of the manganese(I) carbonyl complex, [(κ2-N,N′-Piso)Mn(CO)4] (reactions with CO), and the manganese(III)-μ-oxo complex, [{(κ2-N,N′-Piso)Mn(μ-O)}2] (reactions with O2 and N2O). These results indicate that [{(N-,η3-arene-Piso)Mn(μ-H)2}2] can act as a “masked” source of an amidinato-manganese(I) fragment in synthetic transformations.

Graphical abstract: Stabilisation of carbonyl free amidinato-manganese(ii) hydride complexes: “masked” sources of manganese(i) in organometallic synthesis

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Article information


Submitted
16 Nov 2015
Accepted
04 Dec 2015
First published
08 Dec 2015

Dalton Trans., 2016,45, 1436-1442
Article type
Paper

Stabilisation of carbonyl free amidinato-manganese(II) hydride complexes: “masked” sources of manganese(I) in organometallic synthesis

L. Fohlmeister and C. Jones, Dalton Trans., 2016, 45, 1436 DOI: 10.1039/C5DT04504E

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