Abstract
Pincer-supported iron complexes of the form [(iPrPNHP)Fe(H)(HBH3)(CO)] (iPrPNHP = HN(CH2CH2PiPr2)2), [(iPrPNHP)Fe(H){OC(O)H}(CO)], [(iPrPNP)Fe(H)(CO)]; iPrPNP = N(CH2CH2PiPr2)2–) have proven to be a privileged class of catalysts for hydrogenation and dehydrogenation reactions. Here, the synthesis, characterization, and reactivity of a family of complexes related to these species, in which the ancillary carbonyl ligand has been replaced with an aryl isonitrile ligand, is described. The complexes [(iPrPNHP)Fe(Cl)2(C≡NR)] (R = 2,6-dimethylphenyl (1a), 4-methoxyphenyl (1b)) were prepared in good yield through the dropwise addition of the aryl isonitrile to an in situ generated solution of [(iPrPNHP)Fe(Cl)2]. If the aryl isonitrile was added too quickly, significant amounts of the cationic bis(isonitrile) complexes [(iPrPNHP)Fe(Cl)(C≡NR)2][Cl] (R = 2,6-dimethylphenyl (2a); 4-methoxyphenyl (2b)) were also formed. Treatment of 1a with excess NaBH4 generated [(iPrPNHP)Fe(H)(HBH3)(C≡NR)] (3a), but the correspondin...
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