| Abstract: | Hydrogenation of Aromatic Nitriles on the Fe3(CO)9 Cluster The μ3-nitrile bridged clusters Fe3(CO)9(μ3-η2-N≡CR) ( 3 , R = phenyl, p-tolyl, p-anisyl) consume hydrogen upon heating in solution with formation of the acimidoyl- and the alkylideneimido-bridged clusters HFe3(CO)9(μ3-η2-HN=CR) ( 1 ) and HFe3(CO)9(μ3-η2-N=CHR) ( 2 ). These can be obtained in a better way by successive H+ and H– addition with NaBH4 and H3PO4. HFe3(CO)9(μ3-η2-N=CHR) ( 2 ) adds P(OMe)3 with concomitant hydrogen migration to form Fe3(CO)9P(OMe)3(μ3-η1-N–CH2R) ( 6 ). The phosphite-substituted cluster Fe3(CO)8P(OMe)3(μ3-η2-N≡CPh) ( 5 a ) on the other hand is converted by the H+/H– addition to the products HFe3(CO)8P(OMe)3(μ3-η2-HN=CPh) ( 7 a ) and HFe3(CO)8P(OMe)3(μ3-η2-N=CHPh) ( 8 a ). |
