Diamondoid-Type Copper Coordination Polymers Containing Soft Cyclodiphosphazane Ligands

Three novel coordination polymers have been synthesized by reacting cis- and trans-alkyne-appended cyclodiphosphazanes with CuX (X = Br, I) salts. The reaction of cis-[(PhCCP)2(μ-NtBu)2] (1) with CuBr in a 1:3 molar ratio gave a 3D coordination polymer, [{Cu4­(μ3-Br)4}­{(cis-(PhCCP)2­(μ-NtBu)2)­Cu4­(μ2-Br)4­(cis-(PhCCP)2­(μ-NtBu)2)}4]n (3), having diamondoid topology with an unprecedented copper alkyne coordination, whereas the reaction of 1 with CuI in a 1:4 molar ratio afforded a 1D polymeric complex, [{Cu4­(μ3-I)4}­(NCCH3)2­{cis-(PhCCP)2­(μ-NtBu)2}2]n (4). In contrast, the reaction of trans-[(PhCCP)2(μ-NtBu)2] (2) with CuI was found to be independent of stoichiometry and afforded a 3D coordination polymer, [{Cu4­(μ3-I)4}­{trans-(PhCCP)2­(μ-NtBu)2}2]n (5), exclusively.