0000000000379004
AUTHOR
Eva Guillamón
Insight into the mechanism of diazocompounds transformation catalyzed by hetero cuboidal clusters [Mo3CuQ4(MeBPE)3X4]+, (Q=S, Se; X=Cl, Br): The catalytically active species
Abstract Two enantiomerically pure trinuclear compounds of formula (P)-[Mo3S4{(R,R)-Me–BPE}3Br3]Br and (P)-[Mo3Se4{(R,R)-Me–BPE}3Cl3]Cl, (P)-1b.Br and (P)-1c.Cl, respectively, have been synthesized in a good yield and a stereospecific manner by excision of polymeric [Mo3Q7X4]n (Q = S or Se, X = Cl or Br) phases with (R,R)-Me–BPE{1,2-bis[(2R,5R)-2,5-(dimethylphospholan-1-yl)]ethane}. They have been transformed into chiral hetereo cuboidal compounds [Mo3S4{(R,R)-Me–BPE}3Br3]PF6, (P)-2b.PF6, and [Mo3Se4{(R,R)-Me–BPE}3Cl3]PF6, (P)-2c.PF6, by reaction with copper salts. All these compounds have been characterized by 31P NMR, IR, UV–Vis, mass spectrometry, elemental analysis, and chiral dichroism…
Unprecedented Stereoselective Synthesis of Catalytically Active Chiral Mo3CuS4 Clusters
Cluster excision of polymeric {Mo3S7Cl4}n phases with chiral phosphane (+)-1,2-bis[(2R,5R)-2,5-(dimethylphospholan-1-yl)]ethane ((R,R)-Me-BPE) or with its enantiomer ((S,S)-Me-BPE) yields the stereoselective formation of the trinuclear cluster complexes [Mo3S4{(R,R)-Me-BPE}3Cl3]+ ([(P)-1]+) and [Mo3S4{(S,S)-Me-BPE}3Cl3]+ ([(M)-1]+), respectively. These complexes possess an incomplete cuboidal structure with the metal atoms defining an equilateral triangle and one capping and three bridging sulfur atoms. The P and M symbols refer to the rotation of the chlorine atoms around the C3 axis, with the capping sulphur atom pointing towards the viewer. Incorporation of copper into these trinuclear c…