Synthesis and Structural Characterizations of New Coordination Polymers Generated by the Interaction Between the Trinuclear Triangular SBU [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ and 4,4′-Bipyridine. 3°

The reactions of 4,4′-bipyridine with selected trinuclear triangular copper­(II) complexes, [Cu₃(μ₃-OH)­(μ-pz)₃(RCOO)₂L_<i>x</i>], [pz = pyrazolate anion, R = CH₃(CH₂)_<i>n</i> (2 ≤ <i>n</i> ≤ 5); L = H₂O, MeOH, EtOH] yielded a series of 1D coordination polymers (CPs) based on the repetition of [Cu₃(μ₃-OH)­(μ-pz)₃] secondary building units joined by bipyridine. The CPs were characterized by conventional analytical methods (elemental analyses, ESI-MS, IR spectra) and single crystal XRD determinations. An unprecedented 1D CP, generated through the bipyridine bridging hexanuclear copper clusters moieties, two 1D CPs presenting structural analogies, and two monodimensional tapes having almost exactly superimposable structures, were obtained. In one case, the crystal packing makes evident the presence of small, not-connected pores, accounting for ca. 6% of free cell volume

Interaction of the Trinuclear Triangular Secondary Building Unit [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ with 4,4′-Bipyridine. Structural Characterizations of New Coordination Polymers and Hexanuclear Cu^II Clusters. 2°

By reacting 4,4′-bipyridine (bpy) with selected trinuclear triangular Cu^II complexes, [Cu₃(μ₃-OH)­(μ-pz)₃­(RCOO)₂­(LL′)] [pz = pyrazolate anion; R = CH₃, CH₃CH₂, CH₂CH, CH₂C­(CH₃); L, L′ = Hpz, H₂O, MeOH] in MeOH, the substitution of monotopic ligands by ditopic bpy was observed. Depending on the stoichiometric reaction ratios, different compounds were isolated and structurally characterized. One- and two-dimensional coordination polymers (CPs), as well as two hexanuclear Cu^II clusters were identified. One of the hexanuclear clusters self-assembles into a supramolecular three-dimensional structure, and its crystal packing shows the presence of two intersecting channels, one of which is almost completely occupied by guest bpy, while in the second one guest water molecules are present. This compound also shows a reversible, thermally induced, single-crystal-to-single-crystal transition

Platinum(II) Complexes with Novel Diisocyanide Ligands: Catalysts in Alkyne Hydroarylation

A series of novel diisocyanide ligands (<i>o</i>-CNC₆H₄O)₂Y (diNC-1: Y = P­(O)­Ph; diNC-2: Y = <i>o</i>-C­(O)­C₆H₄C­(O); diNC-3: Y = <i>m</i>-C­(O)­C₆H₄C­(O); diNC-4: Y = C­(O)­C₂H₄C­(O); diNC-5: Y = <i>trans</i>-C­(O)­C₂H₂C­(O)) was successfully synthesized by reaction of lithium 2-isocyanophenate (generated in situ from benzoxazole and <i>n</i>-BuLi) and a diacylic or phosphonic dichloride. The corresponding platinum­(II) complexes of general formula [PtX₂(diNC)]_1,2 (X = Cl, Me; diNC = diisocyanide ligand) were isolated by simple substitution of 1,5-cyclooctadiene in the starting [PtX₂(COD)] complexes. The structure of the complexes, mononuclear or dinuclear, was confirmed by single-crystal X-ray analysis. A dinuclear complex of formula {(μ-diNC)­[<i>cis</i>-PtCl₂(PPh₃)]₂} could also be obtained with the diisocyanide ligand having a rigid fumaryl bridge and consequently the isocyanide moieties pointing in opposite directions. All the complexes were employed as catalysts in the hydroarylation of alkynes, showing generally good activity and selectivity toward the <i>trans</i>-hydroarylation product. With <i>N</i>-methylindole as aromatic substrate the major product was instead a heterocycle:alkyne 2:1 adduct

Coordination Polymers Based on the Trinuclear Triangular Secondary Building Unit [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ (pz = pyrazolate) and Succinate Anion

Reaction conditions (solvent, temperature, pressure) and reagents ratios control the formation of different products from the reactions involving Cu^II, pyrazole (Hpz), and succinate ion (Suc). Three different coordination polymers (CPs) (one of which porous) based on the trinuclear triangular Cu₃(μ₃-OH)­(μ-pz)₃ secondary building unit (SBU), as well as a 1D CP based on the Cu­(Hpz)₂ SBU were obtained. Moreover, a 3D supramolecular network, formed through quite strong H-bonding interactions involving the mononuclear Cu­(HSuc)₂(Hpz)₄ complex, was also synthesized when an excess of H₂Suc was added

Platinum(II) Complexes with Novel Diisocyanide Ligands: Catalysts in Alkyne Hydroarylation

A series of novel diisocyanide ligands (<i>o</i>-CNC₆H₄O)₂Y (diNC-1: Y = P­(O)­Ph; diNC-2: Y = <i>o</i>-C­(O)­C₆H₄C­(O); diNC-3: Y = <i>m</i>-C­(O)­C₆H₄C­(O); diNC-4: Y = C­(O)­C₂H₄C­(O); diNC-5: Y = <i>trans</i>-C­(O)­C₂H₂C­(O)) was successfully synthesized by reaction of lithium 2-isocyanophenate (generated in situ from benzoxazole and <i>n</i>-BuLi) and a diacylic or phosphonic dichloride. The corresponding platinum­(II) complexes of general formula [PtX₂(diNC)]_1,2 (X = Cl, Me; diNC = diisocyanide ligand) were isolated by simple substitution of 1,5-cyclooctadiene in the starting [PtX₂(COD)] complexes. The structure of the complexes, mononuclear or dinuclear, was confirmed by single-crystal X-ray analysis. A dinuclear complex of formula {(μ-diNC)­[<i>cis</i>-PtCl₂(PPh₃)]₂} could also be obtained with the diisocyanide ligand having a rigid fumaryl bridge and consequently the isocyanide moieties pointing in opposite directions. All the complexes were employed as catalysts in the hydroarylation of alkynes, showing generally good activity and selectivity toward the <i>trans</i>-hydroarylation product. With <i>N</i>-methylindole as aromatic substrate the major product was instead a heterocycle:alkyne 2:1 adduct

Coordination Polymers Based on the Trinuclear Triangular Secondary Building Unit [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ (pz = pyrazolate) and Succinate Anion

Reaction conditions (solvent, temperature, pressure) and reagents ratios control the formation of different products from the reactions involving Cu^II, pyrazole (Hpz), and succinate ion (Suc). Three different coordination polymers (CPs) (one of which porous) based on the trinuclear triangular Cu₃(μ₃-OH)­(μ-pz)₃ secondary building unit (SBU), as well as a 1D CP based on the Cu­(Hpz)₂ SBU were obtained. Moreover, a 3D supramolecular network, formed through quite strong H-bonding interactions involving the mononuclear Cu­(HSuc)₂(Hpz)₄ complex, was also synthesized when an excess of H₂Suc was added

Coordination Polymers Based on the Trinuclear Triangular Secondary Building Unit [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ (pz = pyrazolate) and Succinate Anion

Reaction conditions (solvent, temperature, pressure) and reagents ratios control the formation of different products from the reactions involving Cu^II, pyrazole (Hpz), and succinate ion (Suc). Three different coordination polymers (CPs) (one of which porous) based on the trinuclear triangular Cu₃(μ₃-OH)­(μ-pz)₃ secondary building unit (SBU), as well as a 1D CP based on the Cu­(Hpz)₂ SBU were obtained. Moreover, a 3D supramolecular network, formed through quite strong H-bonding interactions involving the mononuclear Cu­(HSuc)₂(Hpz)₄ complex, was also synthesized when an excess of H₂Suc was added

Coordination Polymers Based on the Trinuclear Triangular Secondary Building Unit [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ (pz = pyrazolate) and Succinate Anion

Reaction conditions (solvent, temperature, pressure) and reagents ratios control the formation of different products from the reactions involving Cu^II, pyrazole (Hpz), and succinate ion (Suc). Three different coordination polymers (CPs) (one of which porous) based on the trinuclear triangular Cu₃(μ₃-OH)­(μ-pz)₃ secondary building unit (SBU), as well as a 1D CP based on the Cu­(Hpz)₂ SBU were obtained. Moreover, a 3D supramolecular network, formed through quite strong H-bonding interactions involving the mononuclear Cu­(HSuc)₂(Hpz)₄ complex, was also synthesized when an excess of H₂Suc was added

Coordination Polymers Based on the Trinuclear Triangular Secondary Building Unit [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ (pz = pyrazolate) and Succinate Anion

Reaction conditions (solvent, temperature, pressure) and reagents ratios control the formation of different products from the reactions involving Cu^II, pyrazole (Hpz), and succinate ion (Suc). Three different coordination polymers (CPs) (one of which porous) based on the trinuclear triangular Cu₃(μ₃-OH)­(μ-pz)₃ secondary building unit (SBU), as well as a 1D CP based on the Cu­(Hpz)₂ SBU were obtained. Moreover, a 3D supramolecular network, formed through quite strong H-bonding interactions involving the mononuclear Cu­(HSuc)₂(Hpz)₄ complex, was also synthesized when an excess of H₂Suc was added

New Coordination Polymers and Porous Supramolecular Metal Organic Network Based on the Trinuclear Triangular Secondary Building Unit [Cu₃(μ₃‑OH)(μ-pz)₃]²⁺ and 4,4′-Bypiridine. 1°

The trinuclear triangular Cu^II complex [Cu₃(μ₃-OH)­(μ-pz)₃(HCOO)₂(Hpz)₂] (Hpz = pyrazole) reacts with 4,4′-bipyridine (bpy) yielding a two-dimensional (2D) waved sheets, two three-dimensional (3D) coordination polymers (CPs), as well as a hexanuclear Cu^II cluster, depending on the reagent ratios and reaction conditions. Single crystal X-ray diffraction (XRD) determinations point out that, while CPs crystal structures are not porous, the hexanuclear Cu^II clusters are packed in the solid state generating a stable porous 3D supramolecular network, where two kinds of perpendicular, hydrophobic channels (ca. 4.83 × 5.86 Ų and 4.99 × 4.79 Ų, corresponding to the 24.7% of the total crystal volume) are present. In the “as-synthesized” compound, channels of one kind are empty, while the other ones are occupied by guest bpy molecules which can be removed by soaking the crystals in suitable solvents (benzene, toluene, <i>c</i>-hexane) maintaining intact the crystal skeleton. Moreover, two of the above complexes act as catalysts (or catalyst precursors) in the peroxidative oxidation of cyclohexane