† Based on the presentation given at Dalton Discussion No. 2, 2nd-5th

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In order to elucidate the preferred mode of coordination-( ) or ij6(«•)-we have reacted phosphinine (C5H5P) with the open ferrocene (2,4-Me2-7/5-C5Hj)2Fe. The product, pentakis(7i*-phosphinine)iron (1), was subjected to X-ray structural analysis: 1 crystallizes in the space group P2/n with the cell parameters a = 16.010

The trends in carbon‐sulfur bond length for complexes of 1,4,7‐trithiacyclononane (9S3) provide compelling evidence that CS σ* orbitals accept π‐electron density from the metal. As the metal d‐orbital energy and occupancy increase, this leads ultimately to cleavage of the CS bonds with concomitant release of ethene in the Re and Tc complexes [Eq. (a)].

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