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

Phosphinidene-bridged binuclear complexes

“…Fortunately, more stable derivatives of formula [Co 2 (μ-PR)(μ-κ 1 :κ 1 -dppm)(CO) 6 ] (R = TMP(8a) [16], N i Pr 2 (8b) [18]; dppm = Ph 2 PCH 2 PPh 2 ) were prepared when these reactions were carried out in the presence of the dppm ligand. In contrast, the related Mn compounds [Mn 2 (μ-PR)(CO) 8 ] (R = TMP(9a) [19], N i Pr 2 (9b) [18]), prepared from the reaction of K[Mn(CO) 5 ] with Cl 2 PR, were much more stable than their cobalt analogues, remaining unchanged even after several days in THF solution. All these phosphinidene complexes display symmetrically bridging phosphinidene ligands with a trigonal planar disposition around the P atom, as corroborated by an X-ray study for the PN i Pr 2 -bridged Mn complex, and accordingly they give rise to highly deshielded 31 P resonances (ca.…”

“…Synthesis of binuclear phosphinidene complexes through salt metathesis method 1. 5 ] TMP 53 [19] a Reaction carried out in the presence of dppm, then yielding the phosphinidene complex [Co 2 (μ-PR)(CO) 4 (μ-dppm)].…”

“…The outcome of the reactions of the dimanganese complexes 9a,b with sulphur was dependent on the substituents at the nitrogen atom (Scheme 80) [19]. The P(TMP)-bridged complex 9a yielded the eneacarbonyl derivative 163, with a phosphinidene sulphide ligand in an unusual μ-κ 1 ,κ 2 coordination mode, as confirmed through an X-ray diffraction study, also revealing the absence of intermetallic bond as a result of the presence of an additional CO ligand.…”

Enhanced Nucleophilic Behavior of a Dimolybdenum Phosphinidene Complex: Multicomponent Reactions with Activated Alkenes and Alkynes in the Presence of CO or CNXyl

“…5 Notably, this chemistry has been developed mainly using mononuclear complexes, while the chemistry of phosphinidene‐bridged binuclear complexes has been comparatively little explored until recently,6, 7 in spite of the diverse behavior that it might be anticipated for the different coordination modes of the PR ligands in binuclear environments ( A to C in Figure 1). Recent studies on the ditungsten carbonyl complex [W 2 (μ‐PCp*)(CO) 10 ] (type A ; Cp*=C 5 Me 5 ) have revealed marked electrophilic behavior of the phosphinidene ligand,6a,b and the same can be said of the dimanganese complex [Mn 2 (μ‐PR)(CO) 8 ] (R=N i Pr 2 , tetramethylpiperidyl) 6f,g. In contrast, our own studies on binuclear cyclopentadienyl/carbonyl complexes of iron (type C ) and molybdenum (types A and B ) reveal that these molecules can display reactivity patterns reminiscent of both the nucleophilic and the electrophilic mononuclear complexes, which makes them very promising synthetic intermediates 7…”

Syntheses and Structures of Transition Metal Complexes with Phosphanylphosphinidene Chalcogenide Ligands

“…The unsymmetrical thiophosphinidene complex [Mo 2 Cp 2 {μ-κ 2 P,S :κ 1 P ,η 6 -SPMes*}­(CO) 2 ] reacts with metal carbonyls by cleavage of the P–S bond, which represents a new method for accessing heterometallic complexes with bridging phosphinidene ligands. − Considering the influence of spectator ligands, the majority of the above-discussed phosphinidene complexes should be regarded as nucleophilic. The sulfurization of the electrophilic [Mn 2 (CO) 8 ­(μ-PR)] complexes (R = TMP, i Pr 2 N) follows a different pathway and yields products in which the PS moieties are side-on bound to the metal centers . Recently, we started to study the reactivity of the anionic phosphanylphosphinidene W­(VI) complex [(DippN) 2 ­W­(Cl)­(η 2 -P-P t Bu 2 )]­Li­·3DME toward nucleophilic and electrophilic reagents , and reported a density functional theory (DFT) study on the bonding properties of transitions metal complexes with phosphanylphosphinidene ligands .…”