Polyoxometalate‐like structure of new potassium triphenylsiloxides: [K 6 (OSiPh 3 ) 6 (C 3 H 7 OH)(H 2 O)]·2C 6 H 5 CH 3 and [K 6 (OSiPh 3 ) 6 (H 2 O) 2 ]

The synthesis and structural characterization of two new potassium triphenylsiloxides, namely, aqua(propan‐2‐ol)hexakis(triphenylsilanolato)hexapotassium toluene disolvate, [K 6 (C 18 H 15 OSi) 6 (C 3 H 8 O)(H 2 O)]·2C 7 H 8 , and diaquahexakis(triphenylsilanolato)hexapotassium, [K 6 (C 18 H 15 OSi) 6 (H 2 O) 2 ], are reported. Both compounds crystallize in the triclinic space group P . The structure in each case resembles an alkali metal polyoxometalate‐like structure, in which electrostatic interactions are observed in the metal–oxygen core. Furthermore, both compounds also resemble a reverse micelles‐like architecture, in which the hydrophilic core is enclosed in a hydrophobic shell. The cores of the complexes are flanked by hydrophobic aromatic rings derived from Ph 3 SiO − anions, where intramolecular π‐interactions between the aromatic rings and potassium cations stabilize the cores of the crystals. Moreover, in both structures, the presence of hydrogen bonds is observed; until now, no crystal structures have been described containing K atoms and triphenylsiloxide molecules in which the presence of hydrogen bonds was confirmed. Thus, these coordination entities could be considered as attractive reagents for further synthetic protocols towards heterometallic complexes.