Synthesis and structural analysis of [Ni7] and [Ni6] O,O-Ni clusters

Reaction of [(dme)NiBr 2 ] with fully deprotonated forms of triethylene glycol (teg) and o- isopropoxyphenol [ i PrPhOH] resulted in the formation of two ligand-supported metal clusters [Ni 7 (teg) 6 ]Br 2 ( 1 ) and [Ni 6 ( μ 3 -OH) 2 ( i PrPhO) 8 Br 2 ] ( 2 ). The compounds were characterized by single-crystal X-ray diffraction, IR spectroscopy, UV–vis spectroscopy, and elemental analysis. Cluster 1 is a new example of a homoleptic, centrosymmetric, near-planar hexagonal [Ni₇] assembly that resembles a wheel-like complex supported by doubly deprotonated glycol ligands, while cluster 2 features a [Ni₆] core composed of four fused incomplete cubanes derived from a staggered stacking arrangement of two parallel [Ni 3 ] layers featuring a mixed square pyramidal/octahedral coordination environment. Adjusting the reaction conditions leads to the unique dimer [Ni 2 Na 2 (iPrPhO) 6 (MeCN) 2 ] ( 3 ).