µ-Azido-κ(2) N (1):N (1)-µ-chlorido-bis-[(2-chloro-3-dimethyl-amino-1-phenyl-prop-1-en-1-yl-κ(2) C (1),N)palladium(II)] chloro-form monosolvate.

In the binuclear title complex, [Pd2(C11H13ClN)2Cl(N3)]·CHCl3, each Pd(II) atom has a slightly distorted square-planar geometry being coordinated by a C and an N atom of the 2-chloro-3-dimethyl-amino-1-phenyl-propyl ligand, a bridging Cl atom and an N atom of a bridging end-on azide group. There is a short intra-molecular C-H⋯Cl contact in the complex mol-ecule. In the crystal, the chloro-form solvent mol-ecule is linked to the complex via a C-H⋯π inter-action.

(Benzyl isocyanide-κC (1))chlorido(2-chloro-3-dimethyl-amino-1-phenyl-prop-1-en-1-yl-κ(2) C (1),N)palladium(II).

In the title compound, [Pd(C11H13ClN)Cl(C8H7N)], which crystallized in the chiral space group P212121, the Pd(II) atom is coordinated by two C atoms, a Csp(2) atom of the 2-chloro-3-dimethyl-amino-1-phenyl-prop-1-en-1-yl ligand and a Csp atom from the benzyl isocyanide ligand, as well as an N atom of the ligand and a Cl atom, in a square-planar geometry. In the complex, there is a short C-H⋯Cl hydrogen bond and a C-H⋯π inter-action. In the crystal, mol-ecules are linked via C-H⋯Cl hydrogen bonds, forming chains along the a-axis direction.

Ammonium piperidine-1-carbodithio-ate.

The title compound, NH(4) (+)·C(6)H(10)NS(2) (-), is composed of an ammonium cation and a piperidine-1-carbodithio-ate anion which exhibits positional disorder. The atoms of the ring have a structural disorder and they are divided into two sites, with occupancy factors of 0.584 and 0.426.. In the crystal, the cation and anion are linked by N-H⋯S hydrogen bonds to form an infinite two-dimensional network.

Activation of carbon dioxide by bicyclic amidines.

Activation of the carbon dioxide molecule was achieved using bicyclic amidines (DBU, PMDBD, and DBN). The solution reaction of CO(2) with amidines yielded the corresponding zwitterionic complexes through the formation of a N-CO(2) bond. (13)C NMR data confirmed the carbamic nature of the carbamic zwitterions, DBU-CO(2) and PMDBD-CO(2). However, when these adducts were crystallized, the X-ray analyses of the single crystals were in agreement with bisamidinium bicarbonate salt structures, indicating that structural changes occurred in the crystallization process. The elemental and thermogravimetric analysis data for the carbamic zwitterions, DBU-CO(2) and PMDBD-CO(2), initially obtained by the direct reaction of amidines with CO(2), suggest that these molecules are probably associated with one molecule of water by hydrogen-bond formation (amidinium(+)-COO(-)...H(2)O). A correlation was observed between the thermal stability and the transcarboxylating activity for the amidine-CO(2) complexes. Theoretical calculations of hardness were performed at the B3LYP/cc-pVTZ level of theory and showed concordance with the experimental reactivity of DBU and PMDBD toward CO(2).