29827-46-1

Upstream product

• 21264-30-2 dichloro bis(acetonitrile) palladium(II) 
• 931-53-3 Cyclohexyl isocyanide 
• 80181-60-8 PdCl₂(C₆H₆)(C₆H₁₁NC)2 

Downstream Products

• 115226-88-5 cis-Cl₂(C₆H₁₁NC)Pd{CN(C₆H₁₁)CH₂CH₂S} 
• 63560-38-3 trans-[PdCl(C(NC₆H₁₁)CMeNC₆H₁₁)(PPh₃)2] 

Relevant academic research and scientific papers

Halides Held by Bifurcated Chalcogen-Hydrogen Bonds. Effect of μ(S,N-H)Cl Contacts on Dimerization of Cl(carbene)PdII Species

The reaction of cis-[PdCl2(CNCy)2] (1) with thiazol-2-amines (2-10) leads to the C,N-chelated diaminocarbene-like complexes [PdCl{C(N(H)4,5-R2-thiazol-2-yl)NHCy}(CNCy)] (11-14; 82-91%) in the case of 4,5-R2-thiazol-2-amines (R, R = H, H (2), Me, Me (3), -(CH2)4- (4)) and benzothiazol-2-amine (5) or gives the diaminocarbene species cis-[PdCl2{C(N(H)Cy)N(H)4-R-thiazol-2-yl}(CNCy)] (15-19; 73-93%) for the reaction with 4-aryl-substituted thiazol-2-amines (R = Ph (6), 4-MeC6H4 (7), 4-FC6H4 (8), 4-ClC6H4 (9), 3,4-F2C6H3 (10)). Inspection of the single-crystal X-ray diffraction data for 15-17 and 19 suggests that the structures of all these species exhibit previously unrecognized bifurcated chalcogen-hydrogen bonding μ(S,N-H)Cl and also PdII···PdII metallophilic interactions. These noncovalent interactions collectively connect two symmetrically located molecules of 15-17 and 19, resulting in their solid-state dimerization. The existence of the μ(S,N-H)Cl system and its strength (6-9 kcal/mol) were additionally verified/estimated by a Hirshfeld surface analysis and DFT calculations combined with a topological analysis of the electron density distribution within the formalism of Bader's theory (AIM method) and NBO analysis. The observed noncovalent interactions are jointly responsible for the dimerization of 15-19 not only in the solid phase but also in CHCl3 solutions, as predicted theoretically by DFT calculations and confirmed experimentally by FTIR, HRESI-MS, 1H NMR, and diffusion coefficient NMR measurements. Available CCDC data were processed under the new moiety angle, and the observed μ(S,E-H)Cl systems were classified accordingly to E (E = N, O, C) type atoms.

Cis/trans equilibrium as the way to form Pd carbene catalyst from trans -Isocyanide complex

The behavior of Pd(II) bis-isocyanide complexes in solution was studied for examples of bis-(cyclohexylisocyanide)palladium(II) dichloride (1) and diiodide (2). The equilibrium between isomeric cis- and trans-forms of 1 was observed by NMR and IR spectroscopy. Complex 1 (which has the cis-configuration in the solid state) gives cis-/trans-isomeric mixture after dissolving in CDCl 3 for several days at room temperature. The effect of heating on the equilibration rate was considered. The studied equilibrium leads to a purely cis-structure of Pd carbene complex (3) that was synthesized via the interaction of cis-/trans-isomeric mixture of 1 with benzophenone hydrazone.

Bis(cyclohexyl isocyanide)palladium(II) Halides and Their Benzene Complexes

Bis(cyclohexyl isocyanide)palladium(II) chloride, PdCl2(C6H11NC)2 (1) was prepared from PdCl2.The configuration of the complex 1 is cis with respect to the isocyanides.The isocyano group in one cyclohexyl isocyanide takes axial conformation to chair form cyclohexyl group, while another takes equatorial conformation.By recrystallization of 1 from benzene bis(cyclohexyl isocyanide)palladium(II) chloride-benzene, PdCl2(C6H11NC)2(C6H6)2 (2) was prepared.IR spectrum of 2 shows a characteristics absorption at 700 cm-1 which is due to the benzene incorporated in the complex.Similar benzene complex was also prepared from PdBr2.