Isomerism of Amides Coordinated to Platinum – X-ray Crystal Structure of O-Bonded Acetamide in a Platinum(II) Complex
✍ Scribed by Renzo Cini; Francesco P. Intini; Luciana Maresca; Concetta Pacifico; Giovanni Natile
- Publisher
- John Wiley and Sons
- Year
- 1998
- Tongue
- English
- Weight
- 429 KB
- Volume
- 1998
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
O-bonded amide complexes of platinum(II), which are stable species due to the higher affinity of platinum for nitrogen donors. In contrast O-bonded amides owe their stability to in acetone solution and which undergo solvolysis in neat water with a rate constant as slow as 8.7•10 -5 s -1 , are their kinetic inertness, where a high pH is required for deprotonation of the NH 2 moiety, the leading step in the reported. The structure of a sample compound [Pt(Me 5 dien)-{O-MeC(O)NH 2 }](CF 3 SO 3 ) 2 has been solved by X-ray isomerization process. In the case of the 2-pyridone complex, the O-bonded form is unstable and isomerizes spontaneously diffraction allowing comparison with related N-bonded (amide)platinum complexes. Isomerization from O-amide to to the N-bonded form, due to the higher acidity of the protonated pyridine-like nitrogen atom. Two rotamers are N-amidate species takes place instantaneously under basic conditions. Protonation of the amidate species leads to the N-present in both the N-pyridone and N-pyridonate species. Hindered rotation stems from the steric rigidity of both bonded amide. N-bonded amides, like the N-bonded amidates, represent the thermodynamically preferred rotating moieties [(Me 5 dien)Pt and pyridone/pyridonate].
📜 SIMILAR VOLUMES
In aqueous solution, bis(nucleoside) complexes formed by the reaction of cis-[Pt(NH3)2(H2O)2]2+ with an excess of either adenosine (ado) or a mixture of adenosine and guanosine (guo) undergo a slow N7--> N1 linkage isomerisation in the adenine moiety. The isomerisation probably involves the breaking