A series of hydridoplatinum(II) complexes stabilized with tribenzylphosphines: their preparation,and an empirical approach to the mutual influence of ligands |
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Authors: | Takeshi Miyamoto |
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Affiliation: | Department of Chemistry, Faculty of Science, The University of Tokyo, Hongo 7-3-1, Tokyo 113 Japan |
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Abstract: | The preparation, IR and NMR spectra of 123 platinum hydrides of the general formula, trans-PtHX(PBz3)2 or trans-PtHL(PBz3)2BPh4 (X = a uninegative anionic ligand, L = a neutral donor molecule, Bz = benzyl), are described. Neutral platinum hydrides have been synthesized by the reduction of trans-PtCl2-(PBz3)2 with NaBH4, by the Michaelis—Arbuzov rearrangement, or by metathesis. Cationic hydridoplatinum(II) complexes are obtained from the reaction of trans-PtHX(PBz3)2 (X = Cl or NO3) with a donor molecule (L) in the presence of NaBPh4, or by coordinating a donor molecule through use of PtH(PBz3)2BPh4 · CH2Cl2. The observed trends in ν(PtH), τ(H), 1J(PtH) and 1J(PtP) in a series of the hydridobenzylphosphineplatinum(II) complexes are discussed in terms of “trans- or cis-influences”, defined as the ability of a ligand to weaken the bond trans or cis to itself. The data support the view that a donor atom trans to the hydridic ligand is important in determining the strength of the PtH bond in this series. Some remarks on the distinctive characteristics of some complexes, e.g., dissociation of coordinated cycloalkanone from platinum(II) or stereochemical non-rigidity of the sym-dimethylurea ligand, are included. Tricyclohexylphosphine analogs also have been prepared for comparison. |
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