Synthesis of σ-π-phosphinidene sulfide complexes [Mn2(CO)n(μ-η1,η2-P(NR2)double bond; length as m-dashS)] (n = 8, 9) via direct sulfuration of electrophilic μ-phosphinidenes and photochemical transformation to a trigonal prismatic Mn2P2S2 cluster

The μ-phosphinidene complexes [Mn2(CO)8{μ-P(TMP)}] (1) (TMP = tetramethylpiperidyl) and [Mn2(CO)8{μ-P(NiPr2)}] (2) react with elemental sulfur to form rare phosphinidene sulfide complexes [Mn2(CO)9{μ-η1,η2-P(TMP)double bond; length as m-dashS}] (3) and [Mn2(CO)8{μ-η1,η2-P(NiPr2)double bond; length as m-dashS}] (4), respectively. Photolysis of 3 results in the unprecedented conversion to [Mn2(CO)6(μ-{κPκ2S}2-(TMP)(S)P–P(S)(TMP)] (5), which contains a novel 10-electron donor diphosphene disulfide ligand (TMP)(S)P–P(S)(TMP).