The synthesis of, and characterization of the dynamic processes occurring in Pd(II) chelate complexes of 2-pyridyldiphenylphosphine

Dalton Transactions : an International Journal of Inorganic Chemistry
Jianke LiuAlexander Steiner

Abstract

Pd(II) complexes in which 2-pyridyldiphenylphosphine (Ph(2)Ppy) chelates the Pd(II) centre have been prepared and characterized by multinuclear NMR spectroscopy and by X-ray crystallographic analysis. trans-[Pd(kappa(1)-Ph(2)Ppy)(2)Cl(2)] is transformed into [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)Cl]Cl by the addition of a few drops of methanol to dichloromethane solutions, and into [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)Cl]X by addition of AgX or TlX, (X = BF(4)(-), CF(3)SO(3)(-) or MeSO(3)(-)). [Pd(kappa(1)-Ph(2)Ppy)(2)(p-benzoquinone)] can be transformed into [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)(MeSO(3))][MeSO(3)] by the addition of two equivalents of MeSO(3)H. Addition of further MeSO(3)H affords [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)PpyH)(MeSO(3))][MeSO(3)](2). Addition of two equivalents of CF(3)SO(3)H, MeSO(3)H or CF(3)CO(2)H and two equivalents of Ph(2)Ppy to [Pd(OAc)(2)] in CH(2)Cl(2) or CH(2)Cl(2)-MeOH affords [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)X]X, (X = CF(3)SO(3)(-), MeSO(3)(-) or CF(3)CO(2)(-)), however addition of two equivalents of HBF(4).Et(2)O affords a different complex, tentatively formulated as [Pd(kappa(2)-Ph(2)Ppy)(2)]X(2). Addition of excess acid results in the clean formation of [Pd(kappa(2...Continue Reading

References

Jul 13, 2000·Accounts of Chemical Research·G Helmchen, A Pfaltz
Dec 26, 2001·Chemical Reviews·S Niu, M B Hall
Apr 8, 2004·Proceedings of the National Academy of Sciences of the United States of America·Andreas Pfaltz, William J Drury
May 22, 2004·Chemical Communications : Chem Comm·Jianke LiuRobin Whyman
Jul 14, 2006·Organic Letters·Remko J DetzJan H van Maarseveen
Apr 30, 2008·Journal of Computational Chemistry·Zdenek ChvalJaroslav V Burda

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Citations

Mar 8, 2016·Journal of the American Chemical Society·Kyle T Horak, Theodor Agapie
Dec 7, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Timothy A ShuttleworthHazel A Sparkes
Feb 12, 2020·Organic Letters·Wenlong RenYian Shi

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