Experimental study demonstrates the synthesis and rotational dynamics of sterically crowded phosphametallocenes, highlighting pathways for novel phosphorus-based ligand design.
New sterically crowded phosphaferrocene and ‐ruthenocene derivatives were synthesized via the 2,5‐bis(trimethylsilyl)phospholide anion 5. Their reactivity with regard to the exchange of the Me3Si groups for other functional groups was examined. X‐ray structures were determined for the mono‐ (6) and the 1,1′‐diphosphaferrocene (8). The activation barrier for ring–ring rotation in 8 was determined by NMR spectroscopy and supported by DFT calculations. Attempts to prepare 2,5‐difunctional phosphaferrocenes through electrophilic substitutions were unsuccessful, but yielded en route a new bidentate P,P ligand (3) and its Mo(CO)4 complex, which were both characterized by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
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Loschen et al. (2006) studied this question.
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