[2+3] Cycloaddition Reactions of Azido Metal Complexes and Crystal Structure of the Cycloadduct of (Ρh₃Ρ)₂Pd(Ν₃)₂ with Benzonitrile

Abstract

Cycloaddition reactions of (R3P) 2M(N3)2 (M = Pd, Pt) with organic nitriles, thiocyanates, isothiocyanates, dimethylacetylenedicarboxylate and carbon disulphide are described; an X-ray analysis of the crystal structure of bis (5-phenyltetrazolato) -bis (triphenylphosphine) palladium (II) is summarised and related to isomerism of the complex in solution.

Platinum(II)‐Promoted [2+3] Cycloaddition of Azide with 4‐Cyanobenzaldehyde, a Schiff Base Derivative or Dicyanobenzenes To Give Formyl‐, Amino(imino)‐ or Cyano‐Functionalized Tetrazolato Complexes

“…[16] For example, we recently reported [17,18] that the diazido complexes cis-[Pt (N 3 2 ] have been reported previously. [19] A trans-azido to cis-tetrazolato conversion is known [20] for a palladium(II) centre. Apart from N 2 N 2 -bonded bistetrazolate complex 3a, the described reaction leads also to the formation of a smaller amount (ca.…”

Structure of a complex of palladium(II) chloride and 5-phenoxy-1-phenyltetrazole co-crystallized with 1,2-dichloroethane solvent

“…The square-planar complex reported here, coordinated through the N(3) atom, appears to be yet another variation similar to the o complex formed with palladium bis(5-phenyltetrazolate) and triphenylphosphine (Kreutzer et al, 1972).…”

“…Thus ZnCl 2 forms a tetrahedral complex with 1-methyltetrazole in which the N(4) atom is coordinated to zinc (Baenziger & Schultz, 1971). Other complexes are square planar or octahedral (Ansell, 1973;Kreutzer, Weis, Boehme, Kemmerich, Beck, Spencer & Mason, 1972) or tetrahedral (Gaughan, Bowman & Dori, 1972) (Motherwell & Clegg, 1978).…”

Azide Chemistry – An Inorganic Perspective, Part II[‡] [3+2]‐Cycloaddition Reactions of Metal Azides and Related Systems

“…de [285a] substitution products X-ray (R = Ph) [285b] see text (1.7. ) [Ru(N 3 )(Tp)(NCMe) [26, 30c,171,172]) [142] www.zaac.wiley-vch.de The disproportional length of this chapter is no accident. The chemicals it is dealing with, viz.…”

“…by increasing the electron density on the azide. [142,171] More detailed kinetic studies on the system [M(N 3 ) 2 L 2 ]/nitrile (M = Pd, Pt; L = phosphine), however, were faced with problems affecting the accuracy of the data, one being the two consecutive reactions of the two N 3 ligands whose rather different rates (k' obsd ϾϾ k'' obsd ) allow azido(tetrazolato) intermediates, e.g. cis-[Pt(N 3 )(N 4 CC 6 H 4 -4-NO 2 ) (PPh 3 ) 2 ], to be trapped.…”