Preparation and Crystal Structure of Copper(I) Carbonyl Hydrogensulfate, obtained by Carbonylation in Sulphuric AcidDedicated to Professor Joachim Strähle on the Occasion of his 65th Birthday

Abstract

The hydrogensulfato-carbonyl derivative [Cu(CO)-(SO 4 H)] n , as obtained from the Cu 2 O/ H 2 SO 4 /CO system and recrystallized from H 2 SO 4 /(CH 3 O) 2 SO 2 has been shown to possess a crystal structure organised in infinite chains built up by corner sharing of {CuO 3 (CO)} and {S(OH)O 3 } tetrahedra. The chains are connected by hydrogen bonds in layers, with CO groups leaning

Copper(I) Chloride Carbonyl Polymers

“…Bond lengths for Cu−C are 1.811(5), 1.819(3), and 1.828(4) Å and for C⋮O are 1.108(5), 1.120(4), and 1.126(5) Å for 3a − c , respectively. These values are well within the range of known copper carbonyl species (Cu−C−O range 169.2−180.0°, Cu−C range 1.660−1.968 Å, C⋮O range 1.043−1.198 Å). − Dihedral angles (C−Cu···Cu−C) between carbonyls on either side of a DABCO ligand are approximately 89.6° and those on either side of a Pip ligand are 68.6°, while those across a Cu 2 Cl 2 dimer are exactly 180°. Since all non-hydrogen atoms in 3c except chlorines and the ring carbons lie on the ac plane, all C−Cu···Cu−C dihedral angles for both carbonyls and DMP methyls are 180°.…”

“…As part of our ongoing studies of Cu(I) coordination polymers, we are investigating the reactions of copper(I) halides with bridging ligands in the presence of carbon monoxide. Numerous Cu(I)−carbonyl complexes are known; − however, only a few polymeric crystal structures containing Cu−CO have been reported. These include that of CuCl(CO) itself, which forms a hexagonal honeycomb layer structure via triply bridging chloride .…”

“…These include that of CuCl(CO) itself, which forms a hexagonal honeycomb layer structure via triply bridging chloride . The use of polydentate anions such as ethyl sulfonate, hydrogen sulfonate, and trichloroacetate with Cu(CO) + produces chain structures . Finally, [Cu(CO)(NCMe)(1,2-di-2-pyridylethylene)] + represents the only reported nitrogen ligand-bridged polymer of Cu(CO) …”

Structure and Bonding in Copper(I) Carbonyl and Cyanide Complexes

“…Uncharacteristically for the soft copper(I) ion, the CuCO unit is often found coordinated to the oxygen donor anions: alkoxide, − carboxylate, sulfonate, and phosphonate . These complexes, which are usually formed under 1 atm of CO, form oligomers and polymers, such as III – V . , The cubane geometry reflected in III is very common for Cu(I), most commonly being encountered with μ 3 -halide corners.…”

Organic-Ligand-Supported Two-Dimensional Carbonyl-Bridged Copper(I) Polymers

“…On the other hand, only a limited number of copper(I) coordination polymers containing a Cu−CO unit have been structurally characterized. All reported copper(I) carbonyl polymers with polydentate ligands, either with N-containing bridging ligands such as diazabicyclo[2.2.2]octane, piperazine, N , N ‘-dimethypiperazine, and 1,2-di-2-pyridylethylene 11c,f or with polyoxygen anions such as ethyl sulfonate, hydrogen sulfate, and trichloroacetate, 11a,d,e exhibit chain structures. Only [CuCl(CO)] n , a compound without a supporting organic ligand, shows a hexagonal honeycomb layer structure,11b and it represents the only reported two-dimensional copper(I) carbonyl polymer.…”