Reductive reactivity of a Zn(I)-Zn(I)-bonded compound toward white phosphorus and beyond

This work reports the selective reduction of a number of small molecules by a Zn(I) Zn(I)-bonded compound. Reaction of dizinc compound [L2Zn2] [L = CH3C(2,6-iPr(2)C(6)H(3)N)CHC(CH3)(NCH2CH2PPh2)] with white phosphorus generated a trimetallic cluster [(LZn)3(mu, k(2): k(2): k(1)-P-7)], which contained a zinc-coordinated Zintl ion [P-7](3-). The low valent Zn(I) compound [L2Zn2] could also reduce 1-azidoadamantane and diphenyl disulfide to selectively afford Zn(II) hexazene complex [L2Zn2(mu-1,6-Ad(2)-N-6)] and thiolate derivative [LZnSPh], respectively. In contrast, oxidation reaction selectively occurred at the pendant phosphine of ligand backbone when reacting [L2Zn2] with elemental sulfur, whereas Zn(I) Zn(I) bond remained intact.