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The synthesis of a highly unsymmetrical, chiral oxometallocubane anion [{(π‐C3H5)Mo(CO)2}4(µ3‐OH)3(µ3‐O)]− built up from organometallic moieties and oxo ligands is described. Its structure was investigated not only in the solid state (X‐ray diffraction analysis) but also in solution applying modern sophisticated NMR techniques. It was thereby possible to identify a trigonal twist rearrangement as the process responsible for the fluxional behaviour of this compound in solution: the (π‐allyl)Mo moieties are highly mobile, rotating on the “oxo surface” even at −65 °C. This complex can be regarded as a suitable model for (π‐allyl)Mo units incorporated into molybdenum oxide surfaces.

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NMR‐NOE analysis of the three compounds (RRS/SSR)‐CH3C(CH2PPhBz)3Mo(CO)3 (1), (RRR/SSS)‐CH3C(CH2PPhBz)3Mo(CO)3 (2), and (RRR/SSS)‐CH3C[CH2P(m‐Xyl)Bz]3Mo(CO)3 (3), leads to experimental values for a number of intramolecular H···H contacts in each case. By the very nature of the NOE method, and with the type of molecules studied here, these values have to be understood as a Boltzmann weighted average over all the conformations accessible to the molecules in solution. – A Boltzmann weighted force field approach is used to predict these values on the basis of sets of force field parameters derived earlier for this class of compounds. The agreement between observed and calculated NOE distances is highly satisfactory in each case (rms = 0.2 Å to 0.3 Å). By a statistical analysis it is shown that the predictions made by applying this Boltzmann weighted force field approach are highly significant. There is only a chance of 3 in 100 000 that this quality of prediction might be obtained by chance. This is taken as a validation, albeit indirect, of the energy scale reproduced by the force field parameters as developed. The methods described give a detailed insight into the conformational flexibility of molecules of the type studied. Solid state structures of the molecules are also correctly modelled by the force field used.

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