Millard Shaun, Fothergill Jenny W, Anderson Zoe, Brown Eric C, King Matthew D, Colson Adam C
Department of Chemistry and Biochemistry , Boise State University , Boise , Idaho 83725 , United States.
Micron School of Materials Science and Engineering , Boise State University , Boise , Idaho 83725 , United States.
Inorg Chem. 2019 Jun 17;58(12):8130-8139. doi: 10.1021/acs.inorgchem.9b00917. Epub 2019 May 24.
An investigation of supramolecular phenomena involving zerovalent transition metal complexes was facilitated by the production of the ditopic isocyanide ligand 1,3-bis( p-isocyanophenyl)urea, which was synthesized via substoichiometric phosgenation of 4-isocyanophenylamine and used to coordinate group VI metal carbonyl fragments. The resulting binuclear organometallic complexes were observed to pack into ladder-like anisotropic arrays in the solid state. Crystallographic and computational evidence suggests that this packing motif can be attributed to a combination of intermolecular π-π and urea-π interactions. Similar to other N, N'-diarylureas bearing electron-withdrawing groups, 1,3-bis( p-isocyanophenyl)urea and the organometallic complexes prepared therefrom also exhibit an affinity toward anion binding in nonaqueous solution. Equilibrium constants ( K) for the formation of host-guest complexes between the organometallic derivatives of 1,3-bis( p-isocyanophenyl)urea and chloride, nitrate, and acetate anions exceed 10, 10, and 10 M, respectively.
通过制备双齿异腈配体1,3-双（对异氰基苯基）脲，促进了对涉及零价过渡金属配合物的超分子现象的研究。该配体通过4-异氰基苯胺的亚化学计量光气化反应合成，并用于配位第VI族金属羰基片段。观察到所得的双核有机金属配合物在固态下堆积成梯状各向异性阵列。晶体学和计算证据表明，这种堆积模式可归因于分子间π-π和脲-π相互作用的组合。与其他带有吸电子基团的N,N'-二芳基脲类似，1,3-双（对异氰基苯基）脲及其制备的有机金属配合物在非水溶液中也表现出对阴离子结合的亲和力。1,3-双（对异氰基苯基）脲的有机金属衍生物与氯离子、硝酸根离子和醋酸根离子形成主客体配合物的平衡常数（K）分别超过10、10和10 M。
