Solvent Control of the Thiocyanate's Bonding Mode in Dithiocyanato[bis(diphenylphosphino)alkyl or aryl]-Palladium (II) Complexes

Abstract The effects on the linkage isomeric distribution in the solid state created by recrystallizing eight dithiocyanato[bis(diphenylphosphino)alkyl or aryl]palladium(II) complexes from each of eight different solvents (chloroform, methylene chloride, acetone, ethanol, methanol, nitromethane acetonitrile, and N,N-dimethylformamide) have been determined. Five of the complexes ([Pd(Ph2PCH2PPh2)(SCN)2], [Pd(Ph2P(CH2)2PPh2)(NCS)(SCN)], [Pd(Ph2P(CH2)4PPh2)(NCS)(SCN)], [Pd(Ph2P(CH2)5PPh2) (NCS)2]2, and [Pd(α, α'-bis(diphenylphosphino)-o-xylene)(NCS)(SCN)]) retained their initial thiocyanate bonding modes through each of the recrystallizations. However, the remaining three complexes ([Pd(Ph2P(CH2)3PPh2)(NCS)(SCN)], [Pd(cis-bis(diphenylphosphino)benzene)(NCS)(SCN)], and [Pd(cis-1,2-bis(diphenylphosphino)ethylene)(thiocyanate)2]) experienced dramatic alteration of their original thiocyanate bonding modes as a consequence of recrystallization from some solvents.

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