Synthesis of sigma-pi-phosphinidene sulfide complexes [Mn-2(CO)(n)(mu-eta(1),eta(2)-P(NR2)=S)] (n=8,9) via direct sulfuration of electrophilic mu-phosphinidenes and photochemical transformation to a trigonal prismatic Mn2P2S2 cluster

摘要

The mu-phosphinidene complexes [Mn-2(CO)(8){mu-P(TMP)}] (1) (TMP = tetramethylpiperidyl) and [Mn-2(CO)(8){mu-P((NPr2)-Pr-t)}] (2) react with elemental sulfur to form rare phosphinidene sulfide complexes [Mn-2(CO)(9){mu-eta(1), eta(2)-P(TMP)=S}] (3) and [Mn-2(CO)(8){mu-eta(1), eta 2-P((NPr2)-Pr-t)=S}] (4), respectively. Photolysis of 3 results in the unprecedented conversion to [Mn-2(CO)(6)(mu-{kappa P kappa S-2}(2)-(TMP)(S)P-P(S)(TMP)] (5), which contains a novel 10-electron donor diphosphene disulfide ligand (TMP)(S)P-P(S)(TMP). (c) 2006 Elsevier B.V. All rights reserved.