Nickelatetrazoles as Intermediates in the Course of the Photolysis of Nickel(II) Azido Complexes? – A Theoretical Study

✍ Scribed by Dörte Kurz; Horst Hennig; Joachim Reinhold

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: German
• Weight: 192 KB
• Volume: 626
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/(sici)1521-3749(200002)626:2<354::aid-zaac354>3.0.co;2-a

✦ Synopsis

The primary photoreactions due to charge transfer excitation of d 8 transition metal complexes of [MP 2 (N 3 ) 2 ] constitution (P 2 : mono-or diphosphane ligands) are strongly influenced by the central ion. While [MP 2 (N 3 ) 2 ] complexes of both palladium(II) and platinum(II) yield primarily the corresponding metal(I) species and azidyl radicals, nickel(II) complexes of the same constitution lead to intermediate generation of nitrenes as has been indirectly shown by various scavenging reactions. During the course of the succeeding reactions, the intermediate generation of nickelatetrazoles is assumed. Both nitrene and metallatetrazole intermediates could not be identified directly so far. Therefore, the pro-posed reaction pathway has been modeled theoretically to get indications regarding the probability of the formation of such intermediates. Based on density functional theory (DFT) calculations, the energetics of the proposed pathway is compared with those of possible other pathways. The calculations support the proposed reaction pathway and point to possible reasons for the different behaviour of nickel(II) compared to palladium(II) and platinum(II).