From phosphanylphosphaalkenes to coordination copper and silver polymers containing P-P bonds.

This study was focused on the activation of the CP bond via reactions of Ph2CP-PtBu2 (1) with 1,6-hexanediol and selected dithiols (1,4-butanedithiol, 1,4-benzenedithiol and 1,4-benzenedimethanethiol). These reactions proceed according to a 1,2-addition mechanism, providing new compounds with formulas {(Ph)2(H)C-P-PtBu2}{μ2-(O-(CH2)6-O)}{tBu2P-P-C(H)(Ph)2} (2), {(Ph)2(H)C-P-PtBu2}{μ2-(S-(CH2)4-S)}{tBu2P-P-C(H)(Ph)2} (3a), {(Ph)2(H)C-P-PtBu2}{μ2-(S-C6H4-S)}{tBu2P-P-C(H)(Ph)2} (3b), and {(Ph)2(H)C-P-PtBu2}{μ2-(S-CH2-C6H4-CH2-S)}{tBu2P-P-C(H)(Ph)2} (3c). Next, the reactions of 3a and 3c with metal chlorides led to the growth of desired coordination polymers of copper(I) and silver(I). All the obtained compounds remained stable under atmospheric conditions.