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| - Theoretical Investigation of the Apparently Irregular Behaviorof Pt−Pt Nuclear Spin−Spin Coupling Constants
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| - One-bond Pt−Pt nuclear spin−spin coupling constants J(Pt−Pt) for closely related dinuclear Ptcomplexes can differ by an order of magnitude without any obvious correlation with Pt−Pt distances. Asrepresentative examples, the spin−spin couplings of the dinuclear PtI complexes [Pt2(CO)6]2+ (1) and[Pt2(CO)2Cl4]2- (2) have been computationally studied with a recently developed relativistic density functionalmethod. The experimental values are 1J(195Pt−195Pt) = 5250 Hz for 2 but 551 Hz for 1. Many other examplesare known in the literature. The experimental trends are well reproduced by the computations and can beexplained based on the nature of the ligands that are coordinated to the Pt−Pt fragment. The differencefor J(Pt−Pt) of an order of magnitude is caused by a sensitive interplay between the influence of differentligands on the Pt−Pt bond, and relativistic effects on metal−metal and metal−ligand bonds as well as on“atomic orbital contributions” to the nuclear spin−spin coupling constants. The results can be intuitivelyrationalized with the help of a simple qualitative molecular orbital diagram.
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