Complexes with Organic Halides. The presence of aryl ligands in the Pd(I) complexes 1 and 2 prompted studies on their reactions with organic halides, which might yield C-C cross-coupling products. Investigating the reactions of 2 with organic halides revealed that cross-coupling products indeed can be formed in the reactions with benzylic halides. The reaction of 2 with methyl 4-(bromomethyl)benzoate takes place quickly at room temperature. In 1 hour, complex 2 was fully consumed and the C-C cross-coupling product 5-CH2C6H4COOMe was produced in 75% NMR yield, along with the m-terphenyl derivative bearing an iso-propenyl group 4, the dehalogenation product p-MeC6H4COOMe, and benzyl radical coupling product MeOOCC6H4CH2CH2C6H4COOMe as the byproducts (Figure ). The cross-coupling product 5-CH2C6H4COOMe has been characterized by NMR spectroscopies, high-resolution mass spectroscopy, and single-crystal X-ray diffraction study (Figure ). In addition to these organic products, palladium black and Pd(II) bromide were observed as the resultant Pd-containing products (Figures and). Complex 2 is also reactive toward methyl 4-iodo-butanate, wherein the NMR yield of the cross-coupling product 5-CH2CH2CH2COOMe is merely 13% and that of the m-terphenyl derivative 4 reaches 76% (Figure ). Different from the reaction with the benzyl bromide, significant amount of black solid was produced in the reaction with the alkyl iodide. Further analysis indicated that it contains mainly the imidazolium salt [HPr]I and palladium black (Figures and). Intriguingly, complex 2 can even react with the aryl iodide 3,5-dimethylphenyl iodide though with decreased rate. In this reaction, the m-terphenyl derivative 4 (94% NMR yield) and 1,3-dimethylbenzene (62% GC yield) were the major products and no cross-coupling product was detected (Figure ). Along with these organic products, the Pd(I) iodide dimer [(IPr)PdI]2 and Pd(II) iodide dimer [(IPr)PdI2]2 were identified as the major palladium-containing products (Figures and). On the other hand, complex 2 is found inert toward 1-octyl bromide, cyclohexyl bromide, and phenyl bromide.