The solubilities of newly synthesized chelating agents, i.e. diethylene glycol bis (2,4,4-trimethyl-1-pentyl) dimethyl diphosphate (EG2TP), diethylene glycol bis (3,5,5-trimethyl-1-hexyl) dimethyl diphosphate (EG2TH), and diethylene glycol dioctyl dimethyl diphosphate (EG2Oct) in supercritical carbon dioxide (scCO(2)) were determined at temperatures ranging from 313 to 333 K and pressures ranging from 9 to 17 MPa. Solubility increases in the order of EG2Oct (MW = 518.56) < EG2TH (MW = 546.61) < EG2TP (MW = 518.56). Solubility parameter and connectivity index of these compounds were calculated and discussed, which indicated that branched side chains of the ligands play an important part in increasing solubility in scCO(2). A semi empirical model proposed by Bartle was used to correlate the experimental data and AARD values were calculated to be 5.2%, 4.4%, and 3.4% for EG2TP, EG2TH, and EG2Oct, respectively. Also the quantum chemical calculation and COSMO-RS method were introduced to estimate the structure effect on the interaction with CO2 by computing the charge density distribution on the surface of these compounds. As expected, better masking effect of the side chains result in higher solubility. (C) 2013 Elsevier B.V. All rights reserved.