Disulfido Metal Carbonyl Complexes Containing Manganese

Abstract

An account of recent studies of the chemistry of new disulfido metal carbonyl complexes containing manganese is presented. The coordination of the disulfido ligands, the nature of reactions at the manganese atom(s) and the nature of insertion reactions at the disulfido ligands are discussed.

Structural, spectroscopic and magnetic properties of M[R2P(E)NP(E)R′2]2complexes, M = Co, Mn, E = S, Se and R, R′ = Ph oriPr. Covalency of M–S bonds from experimental data and theoretical calculations

“…However, the presence of a central metal ion with unpaired electrons is clearly promoting, if not altering, this electron density flow, since, apart from the Co(II) complexes discussed here, similar behaviour is documented in the corresponding series of tetrahedral paramagnetic complexes with Ni(II) (S = 1), as will be reported elsewhere. The participation of paramagnetic metal ions in this electronic channel is further supported by the comparison of the 31 P NMR spectra of the respective series of Zn(II) complexes 8 (this work), Zn iPr L 2 (9) 29 and Zn iPr,Ph L 2 (10), 30 in which the same trend is observed, albeit with minor differences in 31 P chemical shifts that resemble those of the free ligands (Table 4). The diamagnetic nature of Zn(II) seems to allow electron density flow only among the chelate rings.…”

“…9 It should be stressed, however, that Mn is extensively coordinated to sulfides, as for example, in the organometallic complexes reviewed recently. 10 Our research groups are interested in the synthesis of complexes of certain first-series transition elements, with S/Se-containing bidentate ligands LH of the type R 2 P(E)NHP(E)R 2 , E = S or Se. These ligands are considered to be inorganic analogues of b-diketonates, since deprotonation is always accommodated by an extensive delocalization of p electronic density, a phenomenon verified by X-ray crystallography and spectroscopic data.…”

In search for new bonding modes of the methylenedithiolato ligand: novel tri- and tetra-metallic clusters

“…Both Ru1-S1 and Mn1-S1 interatomic distances are in the range of normal single bonds. Although a large number of bimetallic sulphido compounds have been reported in literature, 22 most of them contain a disulphide linkage, as observed for [CpMoMn-(CO) 5 (µ-S 2 )], 23 [{Mn(CO) 3 } 2 (µ-CO)(µ-S 2 )] 24 and [Mn-(CO) 3 -CpNi(µ-S 2 )] 25 or two sulphide ligands as in the case of [Cp*M(PMe 3 )(µ-S) 2 M′(NO)Cp*] 26 (M = Rh, Ir; M′ = Mo, W). 27 Except for a few examples, complexes with a single sulphide bridged between two metal atoms are rare (Chart 2), 28 in particular, complexes only with a mono-sulphide bridge between ruthenium and manganese.…”

Tricarbonylmanganese(i)–lysozyme complex: a structurally characterized organometallic protein

“…{ Tricarbonylmanganese(I) chemistry shows similarities with tricarbonyliron(I) chemistry, namely the formation of thiolate bridged dimetallic hexacarbonyl clusters. 34,35 § All the reaction, purification and characterization steps are carried out in the dark because of the light sensitivity of {Mn(CO) 3 } + -containing species in aqueous solution. " Lysozyme crystals were grown at room temperature within one day using the hanging drop method.…”