Publication details

Dimeric Pd(II) and Pt(II) chloride organometallics with 2-phenylpyridine and their solvolysis in dimethylsulfoxide



Year of publication 2014
Type Article in Periodical
Magazine / Source Journal of Organometallic Chemistry
MU Faculty or unit

Central European Institute of Technology

Web DOI: 10.1016/j.jorganchem.2014.02.016
Field Inorganic chemistry
Keywords palladium; platinum; solvolysis; low-temperature NMR spectroscopy; relativistic DFT calculations; cluster model
Attached files
Description Pd(II) and Pt(II) chloride organometallics with the deprotonated, N(1), C(2’)-chelating form of 2-phenylpyridine (2ppy*), i.e. [Pd(2ppy*)(Cl)]2 (1) and [Pt(2ppy*)(Cl)]2 (2), were studied by 1H, 13C, 15N, and 195Pt NMR in DMF-d7 and by 15N CP/MAS in the solid state. Both dimers immediately decompose in DMSO-d6, however, the products of this process are entirely different for 1 and 2. The cleavage of 1 is unusual among all described [M(2ppy*)(X)]2 dimeric compounds as it yields, most likely, the [Pd(2ppy*)(DMSO-d6)2]+ [Pd(2ppy*)Cl2] ionic pair, whereas 2 is known to undergo a more classical conversion into trans(S,N)-[Pt(2ppy*)(DMSO-d6)Cl]. The conclusions formulated for the above ionic pair were supported by quantum-chemical NMR calculations, calibrated specifically for this class of compounds (geometry optimization tested on molecular cluster, calibration of exact-exchange admixture in the PBE0 functional). The proposed computational approach is shown to be valid and suitable also for similar systems.
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