Substituted cyclopentadienyl ligands—10. Intramolecular steric interactions in [(η-C5H3(SiMe3)2)Mo(CO)2(L)I] |
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| Authors: | Jeremy M Smith David P White Neil J Coville |
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| Institution: | The Centre for Applied Chemistry and Chemical Technology, University of the Witwatersrand, Private Bag 3, Johannesburg, Wits 2050, South Africa |
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| Abstract: | Reaction of C5H4(SiMe3)2 with Mo(CO)6 yielded (η5-C5H3(SiMe3)2)Mo(CO)3]2, which on addition of iodine gave (η5-C5H3(SiMe3)2Mo(CO)3I]. Carbonyl displacement by a range of ligands: L P(OMe)3, P(OPri)3,P(O-o-tol)3, PMe3, PMe2Ph, PMePh2, PPh3, P(m-tol)3] gave the new complexes (η5-C5H3(SiMe3)2 MO(CO)2(L)I]. For all the trans isomer was the dominant, if not exclusive, isomer formed in the reaction. An NOE spectral analysis of (η5-C5H3(SiMe3)2)Mo(CO)2(L)I] L PMe2Ph, P(OMe)3] revealed that the L group resided on the sterically uncongested side of the cyclopentadienyl ligand and that the ligand did not access the congested side of the molecule. Quantification of this phenomenon L P(OMe)3] was achieved by means of the vertex angle of overlap methodology. This methodology revealed a steric preference with the trans isomer (less congestion of CO than I with an SiMe3 group) being the more stable isomer for L P(OMe)3. |
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