The mu(3)-nitrile bridged clusters Fe-3(Co)(9)(mu(3)-eta(2)-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)(mu(3)-eta(2)HN=CR) (1) and HFe3(CO)(9)(mu(3)-eta(2)-N=CHR) (2). These can be obtained in a better way by successive H+ and H- addition with NaBH4 and H3PO4. HFe3(CO)(9)(mu(3)-eta(2)-N=CHR) (2) adds P(OMe)(3) with concomitant hydrogen migration to form Fe-3(CO)(9)P(OMe)(3)(mu(3)-eta(1)-N-CH2R) (6). The phosphite-substituted cluster Fe-3(CO)(8)P(OMe)(3)(mu(3)-eta(2)-N=CPh) (5a) on the other hand is converted by the H+/H- addition to the products HFe3(CO)(8)P(OMe)(3)(mu(3)-eta(2)-HN=CPh) (7a) and HFe3(Co)(8)P(OMe)(3)(mu(3)-eta(2)-N=CHPh) (8a). [References: 13]
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