Diamondoid-Type Copper Coordination Polymers Containing
Soft Cyclodiphosphazane Ligands
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Abstract
Three
novel coordination polymers have been synthesized by reacting <i>cis</i>- and <i>trans</i>-alkyne-appended cyclodiphosphazanes
with CuX (X = Br, I) salts. The reaction of <i>cis</i>-[(PhCCP)<sub>2</sub>(μ-N<sup><i>t</i></sup>Bu)<sub>2</sub>] (<b>1</b>) with CuBr in a 1:3 molar ratio gave a 3D coordination polymer,
[{Cu<sub>4</sub>(μ<sub>3</sub>-Br)<sub>4</sub>}{(<i>cis</i>-(PhCCP)<sub>2</sub>(μ-N<sup><i>t</i></sup>Bu)<sub>2</sub>)Cu<sub>4</sub>(μ<sub>2</sub>-Br)<sub>4</sub>(<i>cis</i>-(PhCCP)<sub>2</sub>(μ-N<sup><i>t</i></sup>Bu)<sub>2</sub>)}<sub>4</sub>]<sub><i>n</i></sub> (<b>3</b>), having
diamondoid topology with an unprecedented copper alkyne coordination,
whereas the reaction of <b>1</b> with CuI in a 1:4 molar ratio
afforded a 1D polymeric complex, [{Cu<sub>4</sub>(μ<sub>3</sub>-I)<sub>4</sub>}(NCCH<sub>3</sub>)<sub>2</sub>{<i>cis</i>-(PhCCP)<sub>2</sub>(μ-N<sup><i>t</i></sup>Bu)<sub>2</sub>}<sub>2</sub>]<sub><i>n</i></sub> (<b>4</b>). In contrast, the reaction of <i>trans</i>-[(PhCCP)<sub>2</sub>(μ-N<sup><i>t</i></sup>Bu)<sub>2</sub>] (<b>2</b>) with CuI was found to be independent
of stoichiometry and afforded a 3D coordination polymer, [{Cu<sub>4</sub>(μ<sub>3</sub>-I)<sub>4</sub>}{<i>trans</i>-(PhCCP)<sub>2</sub>(μ-N<sup><i>t</i></sup>Bu)<sub>2</sub>}<sub>2</sub>]<sub><i>n</i></sub> (<b>5</b>), exclusively
