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 Ph 2 CP-P t Bu 2 (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-P t Bu 2 }{μ 2 -(O-(CH 2 ) 6 -O)}{ t Bu 2 P-P-C(H)(Ph) 2 } (2), {(Ph) 2 (H)C-P-P t Bu 2 }{μ 2 -(S-(CH 2 ) 4 -S)}{ t Bu 2 P-P-C(H)(Ph) 2 } (3a), {(Ph) 2 (H)C-P-P t Bu 2 }{μ 2 -(S-C 6 H 4 -S)}{ t Bu 2 P-P-C(H)(Ph) 2 } (3b), and {(Ph) 2 (H)C-P-P t Bu 2 }{μ 2 -(S-CH 2 -C 6 H 4 -CH 2 -S)}{ t Bu 2 P-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.