Darstellung und Reaktionen von trans‐Cyano(pseudo)halogeno‐bis(triphenylphosphin)platin(II)‐Komplexen

Abstract

Die oxidative Addition von Halogencyan an Pt(PPh3k liefert die gemischten trans-Cyanohalogeno-Komplexe (Ph,P),Pt(X)CN la -c. In diesen kann Halogenid aufgrund des trans-Effekts der Cyanogruppe leicht durch andere anionische Liganden ausgetauscht werden. Die Aid-und Fulminatliganden in ld und g sind besonders reaktiv und lassen sich unter milden Bedingungen in die Iso(thio)cyanato-Gruppe umwandeln. Der durch Cycloaddition von Acetonitril an die Azidgruppe von 1 d gebildete Komplex 4b enthalt N'und N2-gebundene 5-Methyltetrazolat-Liganden.Oberhalb 150°C wird eine N' t* N2 u N3 ci N4-Fluktuation des koordinierten Tetrazolats festgestellt.

Arene ruthenium β-diketonato triazolato derivatives: Synthesis and spectral studies (β-diketones: 1-phenyl-3-methyl-4-benzoyl pyrazol-5-one, acetylacetone derivatives)

“…Evidence obtained to date indicated that both the two isomers [corresponding to coordination at N(1) and at N(2)] were formed simultaneously [26][27][28]44], or else only the N(2) bound isomer was produced exclusively [27,26,45,46]. In contrast to the result published earlier by our group [13], we here obtain only the N(2) bound isomers for both alkoxy substituted acetylenes.…”

Synthesis of arene ruthenium triazolato complexes by cycloaddition of the corresponding arene ruthenium azido complexes with activated alkynes or with fumaronitrile

“…Evidence obtained to date indicates that either of the two isomers N(1) and N(2)-bonded are formed simultaneously [7,12,16,26,27] or only the N(2) bound isomer is produced exclusively [7,12,16,17]. In our cases both the N(1) and N(2) bonded isomers are formed depending on the substituents of the triazolato ring.…”

“…In analogy, a coordinated azide group in metal complexes can also undergo such cycloaddition reactions [6]. Azido complexes undergo [3+2] cycloaddition reactions with nitriles [7][8][9][10][11][12][13][14][15][16][17][18][19] and isonitriles [7,8,[20][21][22][23] to produce tetrazolato complexes. Similar reactions with alkynes produce triazolates complexes [12,[24][25][26]; alkenes, however, react very slowly and mostly afforded mixture of products [8,12].…”

Azide Chemistry – An Inorganic Perspective, Part I Metal ­Azides: Overview, General Trends and Recent Developments

“…Part II). With [Pt(N 3 )(CN)(PPh 3 ) 2 ] showing a strict trans ‐configuration and an even more reactive azide ligand one is rid of the problem 49. The interesting thing about trans ‐[Pt(Me)(N 3 )(PPr i 3 ) 2 ], in contrast, is its synthesis from [Pt(N 3 )Me 3 ] 4 and triisopropylphosphine which proceeds by reductive elimination of ethane 62.…”