The P,P-chelated heteroleptic complex bis[bis(diisopropylphosphino)amido]indium chloride [(i-Pr2P)(2)N](2)InCl was prepared in high yield by treating InCl3 with 2 equiv of (i-Pr2P)(2)NLi in Et2O/tetrahydrofuran solution. Samples of [(i-Pr2P)(2)N](2)InCl in a pentane slurry, a CH2Cl2 solution, or in the solid state were exposed to CO2, resulting in the insertion of CO2 into two of the four M-P bonds to produce [O2CP(i-Pr-2)NP(i-Pr-2)](2)InCl in each case. Compounds were characterized by multinuclear NMR and IR spectroscopy, as well as single-crystal X-ray diffraction. ReactIR solution studies show that the reaction is complete in less than 1 min at room temperature in solution and in less than 2 h in the solid gas reaction. The CO2 complex is stable up to at least 60 degrees C under vacuum, but the starting material is regenerated with concomitant loss of carbon dioxide upon heating above 75 degrees C. The compound [(i-Pr2P)(2)N](2)InCl also reacts with CS2 to give a complicated mixture of products, one of which was identified as the CS2 cleavage product [S=P(i-Pr-2)NP(i-Pr-2)](2)InCl](2)(mu-Cl)[mu-(iPr(2)P)(2)N)].