title: Stabilisation of carbonyl free amidinato-manganese(II) hydride complexes: "masked" sources of manganese(I) in organometallic synthesis.
abstract: Reaction of the amidinato-manganese(ii) bromide complex, [{(κ(2)-N,N'-Piso)Mn(μ-Br)}3(THF)2] (Piso = [(DipN)2CBu(t)](-), Dip = 2,6-diisopropylphenyl), with K[BHEt3] affords the first example of a structurally authenticated amidinato-manganese(ii) hydride complex, [{(N-,η(3)-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)2CBu(t)](-), Dip'' = C6H2Pr(i)2(CPh3)-2,6,4), with K[BHEt3] did not lead to an isolable manganese hydride complex, but its reaction with the magnesium(i) complex, [{((Mes)Nacnac)Mg}2] ((Mes)Nacnac = [(MesNCMe)2CH](-), Mes = mesityl), did. This reaction presumably proceeds via a reactive manganese(i) intermediate, which abstracts hydrogen from a reaction component to give [{(κ(2)-N,N'-Piso'')Mn(μ-H)}3]. A comparison of the reactivities of [{(N-,η(3)-arene-Piso)Mn(μ-H)2}2] and the isomorphous manganese(i) complex, [{(N-,η(3)-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, [(κ(2)-N,N'-Piso)Mn(CO)4] (reactions with CO), and the manganese(iii)-μ-oxo complex, [{(κ(2)-N,N'-Piso)Mn(μ-O)}2] (reactions with O2 and N2O). These results indicate that [{(N-,η(3)-arene-Piso)Mn(μ-H)2}2] can act as a "masked" source of an amidinato-manganese(i) fragment in synthetic transformations.
authors.affiliation: School of Chemistry, Monash University, P.O. Box 23, Melbourne, Victoria 3800, Australia. cameron.jones@monash.edu.
authors.forename: Lea
authors.initials: L
authors.lastname: Fohlmeister
authors.affiliation: School of Chemistry, Monash University, P.O. Box 23, Melbourne, Victoria 3800, Australia. cameron.jones@monash.edu.
authors.forename: Cameron
authors.initials: C
authors.lastname: Jones