Synthesis of σ-π-phosphinidene sulfide complexes [Mn 2(CO) n(μ-η 1,η 2-P(NR 2) [dbnd]S)] ( n = 8, 9) via direct sulfuration of electrophilic μ-phosphinidenes and photochemical transformation to a trigonal prismatic Mn 2P 2S 2 cluster

Abstract

The μ-phosphinidene complexes [Mn 2(CO) 8{μ-P(TMP)}] ( 1) (TMP = tetramethylpiperidyl) and [Mn 2(CO) 8{μ-P(N i Pr 2)}] ( 2) react with elemental sulfur to form rare phosphinidene sulfide complexes [Mn 2(CO) 9{μ-η 1,η 2-P(TMP) S}] ( 3) and [Mn 2(CO) 8{μ-η 1,η 2-P(N i Pr 2) S}] ( 4), respectively. Photolysis of 3 results in the unprecedented conversion to [Mn 2(CO) 6(μ-{κPκ 2S} 2-(TMP)(S)P–P(S)(TMP)] ( 5), which contains a novel 10-electron donor diphosphene disulfide ligand (TMP)(S)P–P(S)(TMP).