CO2 template synthesis of metal formates with a ReO3 net.
The serendipitous discovery of CO2 as a template in the fabrication of ferric formate (1) has led to the preparation of serial metal(III) formates [MIII(HCOO)3.3/4CO2.1/4H2O.1/4HCOOH ]infinity (M = Fe(1), Al (2), Ga (3), and In(4)). The X-ray single-crystal determinations showed that the metals have octahedral geometries and are linked by HCOO- in the anti-anti style into a 3D ReO3 net, where CO2 molecules exist in cages of mmm symmetry and are hydrogen bonded to the formic CH groups. An X-ray powder diffraction (XRD) study revealed that 2 is identical to the documented [Al(HCOO)3.xH2O]. Further synthetic experiments and 13C NMR spectroscopy eventually confirmed that 2 should be formulated as [Al(HCOO)3.3/4CO2.1/4H2O.1/4HCOOH ]infinity, which for decades had been mistakenly given as [AlIII(HCOO)3.xH2O].
Tian
Yun-Qi
YQ
Institute of Chemistry for Functionalized Materials, College of Chemistry and Engineering, Liaoning Normal University, Dalian 116029, China. yqtian@lnnu.edu.cn
Zhao
Yu-Ming
YM
Xu
Hai-Jun
HJ
Chi
Cheng-Yu
CY
D002245:Carbon Dioxide / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005561:Formates / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods / Q000592:standards; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D033362:Powder Diffraction; D012015:Reference Standards; D012211:Rhenium / Q000737:chemistry*; D012680:Sensitivity and Specificity
D005561:Formates; D009942:Organometallic Compounds; D002245:Carbon Dioxide; D012211:Rhenium