Zinc hydroxides and oxides supported by organic ligands: Synthesis and structural diversity

Synthesis, Solid State, Solution and ESI‐MS Studies of Zinc(II) Cluster Complexes with a Branched Mixed Donor Thiolate Ligand

“…Selected bond lengths and angles for 1 are given in Table . The Zn–O bond lengths are modestly longer than known acyclic dizinc µ‐hydroxido complexes , . Each zinc center in the dimeric unit has distorted trigonal bipyramidal coordination geometry with τ ranging from 0.84 to 0.95.…”

“…The Zn‐OH‐Zn motif has been reported in over seven hundred structurally characterized complexes, however relatively few of these complexes have sulfur donors bound to the metal ions. Dinuclear OH‐bridged complexes have been prepared with thiosulfate, tripodal thioimidazolyl ligands, a pentadentate thiosemicarbazone and tridentate mixed NS donor thioether ligands , , .…”

“…However, ESI‐MS exaggerates the relative solution concentration of lower m/z species . Furthermore, geometric constraints prevent L from filling the coordination sphere of Zn(II) and thiolate ligands are more commonly bridging than monodentate in structurally characterized Zn(II) complexes . Hence the peak at 8.72 ppm was assigned to [Zn 2 L 2 ] 2+ ( 2 ).…”

Experimental and Computational Insights into Carbon Dioxide Fixation by RZnOH Species

“…[3] Surprisingly, although a number of zinc complexes supported by multidentate ligands and terminal or bridging hydroxide ligation have been widely investigated experimentally as synthetic analogues of CA, [3,4] related organozinc hydroxide compounds have not been explored in this context. [5] Recently our group demonstrated that RZnOH-type moieties featuring a CO 2 -reactive ZnÀOH group and a proton-reactive ZnÀC bond (Scheme 1 a) possessed the unique ability to fix CO 2 and afforded various zinc carbonate products (Scheme 1 b). These preliminary investigations provided the first example of a structurally characterized alkylzinc hydroxide, tBuZnOH (1), [6] which, in the presence of CO 2 , can form different nanomaterials based on CO 3 2À as a templating ion, for example, ZnCO 3 nanoparticles (NPs) or discrete alkylzinc carbonate cluster 2 (Scheme 1 b).…”

Oxygenation of RZn(N,O)-type complexes as an efficient route to zinc alkoxides not accessible via the classical alcoholysis path

“…15 Compound 3 was characterized spectroscopically and by single crystal X-ray diffraction studies (for details, see the ESI †). Compound 3 crystallizes in the space group C2/c as a tetranuclear cluster with an encapsulation described as a zincoxane (tBu 2 Zn 2 O) moiety entrapped by two m 4 -O 2À oxo ions (Fig.…”