Abstract
The chemistry of the pyrrole-based pincer ligands, RPNP (PNP = anion of 2,5-bis(dialkylphosphinomethyl)pyrrole, R = Cy and t-Bu), with manganese is reported. Metallation of tBuPNP with Mn(II) halide precursors did not afford 1:1 ligand to metal complexes but rather led to the formation of the 2:1 complex, [Mn(κ2-N,P-tBuPNP)2]. Reduction of in situ generated tBuPNP-Mn(II) in the presence of 2,2′-bipyridine generated the apparent, high-spin Mn(I) complex, [Mn(bipy)(tBuPNP)], although metric parameters derived from crystallography demonstrated that the compound is best regarded as containing a Mn(II) ion with a bipy radical anion. Reactions of the Mn(I) precursor, [MnBr(CO)5], with RPNP afforded low-spin Mn(I) complexes of the type [Mn(CO)n(RPNP)] (R = Cy, n = 3; R = t-Bu, n = 2). A third equivalent of CO binds reversibly to [Mn(CO)2(tBuPNP)] but is lost readily. Pincer backbone dehydrogenation of [Mn(CO)n(RPNP)] with 1,4-benzoquinone produced the related complexes, [Mn(CO)n(RdPNP)] (RdPNP = anion of 2,5-bis...
Published Version
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