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Different reference Lewis structures were tried in the NBO analysis in order to assess the stability of the computed M-C π-bond orders. For M = Y, Pd, and Pt, the π-bond order of the M-C bonds was found to be effectively zero and a Lewis structure with three metal-carbon single bonds represents the best description of the metal attachment to the carbon network. This is also the structure arrived at by the NBO program when run in unsupervised mode. For metals of group 4-6, a reference Lewis structure with three metal-carbon double bonds was specified. Although the latter structure does not represent the optimal solution found by the NBO program, all the three bonds contain a significant π component and specification of this Lewis structure does not affect the corresponding σ-bond orders. Finally, for the metals of group 7-9, only the M-C2 bond was found to contain a significant π component and a reference Lewis structure with two metal-carbon single bonds and one double bond was thus specified for these metals.
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