Proton magnetic resonance spectra of platinum(II) complexes. I. Pyramidal configuration and inversion at sulfur in cis-bis(dibenzyl sulfide)dichloroplatinum(II). Temperature and solvent effects on AB chemical shifts

Experimental and theoretical studies on inversion dynamics of dichloro(l-difluoromethionine-N,S)platinum(II) and dichloro(l-trifluoromethionine-N,S)platinum(II) complexes

“…This result lends support to our findings as the two experiments show good agreement despite the use of different experimental methods. A survey of the available literature accounts detailing the thermodynamics of sulfur inversion in various platinum(II)-thioether compounds reveals that the inversion barrier typically falls between 15 and 20 kcal/mol [23,[26][27][28][29], an observation which is supported by our results.…”

Inversion at pyramidal oxygen and sulfur

“…Nonequivalence of the methylene protons in a complex of diethyl sulfide with BH3 has been observed and attributed to hindered inversion about sulfur.12 Hindered inversion has also been observed in platinum chloride complexes of dibenzyl sulfide and the barrier to inversion was found to be 18 kcal/ mol. 14 In the present study nonequivalent methylene protons were observed in the complex between diethyl sulfide and boron trichloride, but not in complexes with boron trifluoride, tantalum pentafluoride, niobium pentafluoride, germanium tetrafluoride, titanium tetrafluoride, aluminum trichloride, and tungsten hexafluoride. Additional Lewis acids and other ethers and sulfides are being investigated to determine the factors which allow nonequivalent methylene protons to be ovserved in complexes of ethers and sulfides.…”

Dynamic Study of Homoleptic Bimetallic Platinum(II) Complexes Bridged by Fluorinated Benzenethiolates

“…The particular molecular conformation depends on a number of factors, such as whether the complexes incorporate a bent or a planar [M 2 (µ-S) 2 ] ring, 1 the relative orientation of the substituents (R) at the sulfur bridging atoms, 2 and the extent of hindered rotation about the R-sulfur bond. 3 Conversion between each of these isomers is accomplished either by flipping of the [M 2 (µ-S) 2 ] ring, 4 hindered rotation about the R-sulfur bond, 5 inversion of configuration at tricoordinated pyramidal sulfur atoms, 6,7 or a combination these processes. 2 Theoretical and experimental studies have shown that the energy differences between planar and bent structures are relatively small (ca.…”