Bis(phosphine) Pd(II)–azido complexes containing heterocyclic ligands: Reactivity toward organic isocyanides

Pseudohalide complexes of palladium(II) containing PCP pincer: Synthesis, characterization, and their antimicrobial activities

“…The n(N 3 ) observed at 2032 cm À1 in Pd(PCP)(N 3 ) (2) is in good accordance with those of reported values at 2031e2035 cm À1 in the Pd(II) azides trans-PdL 2 R(N 3 ) (L ¼ PMe 3 , PEt 3 , P(n-Pr) 3 ) in which the azide ligand is located at trans to the C-bound heterocyclic ligands and at cis to tertiary phosphine ligands in analogy with the PCP pincer complex 2 [74]. The isocyanato complex Pd(PCP)(NCO) (3) exhibits n as (NCO) at 2196 cm À1 in the IR spectrum, which is well consistent with those of previously reported Pd(II) isocyanates trans-Pd(PR 3 ) 2 (Ph)(NCO) (PR 3 ¼ PMe 3 , PEt 3 ) and transPd(PMe 3 ) 2 (C(O)Me)(NCO) at 2180 and 2176 cm À1 , respectively [75].…”

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

“…Note that in the structure of AsPh 4 [Au(CN 4 Pr i ) 4 ] in order to minimize mutual repulsion, the Pr i groups attached to adjacent ( cisoid ) tetrazolato ligands are also oriented in opposite directions ( anti to each other) to give an S 4 isomer in which the transoid Pr i substituents are syn related. [502] A further kind of reaction alternative inducing a novel reactivity is a constant companion of the cycloaddition reaction of azido ligands with isocyanides (CN‐2, 6‐Me 2 C 6 H 3 , CN‐2, 6‐Pr i 2 C 6 H 3 ) in organylpalladium complexes trans ‐[Pd(N 3 )(R)L 2 ] (R = C ‐donor ligand = 2‐thienyl,62 Ph, (2'‐pyridinyl)phenyl‐2 and derivatives ({ C , N } IVa–c ),47,53 2‐(2'‐pyridinyl)thienyl‐3 units in μ‐{ C , N } 2 a and μ‐{ C , N } 2 b ,61 Me 2 NCH 2 C 6 H 4– 2 ({ C , N } II );64 L = e.g. PMe 3 , PEt 3 , PMe 2 Ph) as well as in ortho(cyclo) ‐metallated – mostly cyclopalladated – chelate complexes of the type [Pd(N 3 )(C, N,N)] or [Pd(N 3 )(PR 3 )(C, N)] ((C, N,N) = o ‐metallated 6‐phenyl‐2, 2'‐bipyridyl ({ C , N , N });53 (C, N) = o ‐metallated (2‐pyridyl)aryls,53 2‐(2'‐pyridyl)thienyl units in μ‐{ C , N } 2 a and μ‐{ C , N } 2 b ,61 and dimethylbenzylamine ({ C , N } II )64), viz.…”

“…Further heating to higher temperatures did not convert the 1‐phenyltetrazolato ligand into the corresponding carbodiimide, however, which was attributed to the absence of sterically demanding substituents on the aryl ring (Equation (33)). So, argumentation with steric factors somehow came back through the back door 62 …”

Crystal structure of 4-methylsulfanyl-2-(2H-tetrazol-2-yl)pyrimidine

“…For applications of tetrazolyl-substituted aromatic systems in metal-ligand research, see: Kim et al (2008); Stoessel et al (2010); in drug development, see: Pasternak et al (2012); Biswas et al (2015); in polymer synthesis, see: Yu et al (2008); Sengupta et al (2010). For the synthesis of 4-methylsulfanyl-2-(1H-tetrazol-1-yl)pyrimidine and the title compound, see: Thomann et al (2014 Table 1 Hydrogen-bond geometry (Å , ).…”

“…4-tetrazolylpyrimidines are well reported scaffolds in many bioactive entities. Besides synthetic chemistry, tetrazolyl substituted aromatic systems are also of high interest for example, in metal-ligand research (Kim et al, 2008;Stoessel et al, 2010), drug development (Pasternak et al, 2012;Biswas et al, 2015) and polymer discovery (Yu et al, 2008;Sengupta et al, 2010). Thus, the knowledge of the three dimensional structure of these moieties is of crucial importance for the rational design in these fields of research.…”