Packed in like sardines: Three BF4− ions are packed into the three cavities of an interpenetrated dimer of a coordination cage (see scheme). While the inner BF4− ion is tightly bound inside the central position, the loosely bound outer anions can be replaced with halide anions by an allosteric binding mechanism and a concerted structural change. In particular, Cl− is bound with great affinity.

A breath of fresh air is sufficient for the eightfold S-monooxygenation of an interpenetrated double cage based on eight phenothiazine ligands and four square-planar-coordinated Pd(II) cations. Besides these two cages, which were both characterized by X-ray crystallography, an eightfold S-dioxygenated double-cage was obtained under harsher oxidation conditions.

Silicon(II) bis(trimethylsilyl)amide (LSiN(SiMe(3))(2), L= PhC(NtBu)(2)) (2) has been synthesized by the reaction of LSiHCl(2) with KN(SiMe(3))(2) in 1:2 molar ratio in high yield where 1 equiv of the latter functions as a dehydrochlorinating agent. 2 exhibits a high stability up to 154 °C and can be handled in open air for a short period of time without any appreciable decomposition. An amazing five-membered cyclic silene (3) results from the cleavage of one Si-Me bond of 2 with an adamantyl phosphaalkyne. 3 is the first example of a heavy cyclopentene derivative which consists of four different elements, C, N, Si, and P. Both compounds are characterized by multinuclear NMR spectroscopy, EI-mass spectrometry, and single crystal X-ray diffraction studies.

The base-stabilized bis-silylene (LSi−SiL, L = PhC(NtBu)2) was reacted with benzophenone in a 1:2 ratio in THF, which afforded a Si2O2 four-membered ring, stabilized by bulky amidinato ligands. The most striking phenomenon is the abstraction of oxygen from benzophenone and the simultaneous formation of a silicon carbon bond. The four-membered Si2O2 ring is planar, and both the silicon atoms are five-coordinate. The two silicon atoms are arranged opposite each other in the four-membered Si2O2 ring. Moreover LSi−SiL was treated with N2O to afford two four-membered Si2O2 rings connected with two oxygen atoms. In this structure also the silicon atoms are five-coordinate.

Two structurally characterized manganese [L(2)Mn(CO)(4)](+)[Mn(CO)(5)](-) (1) and rhenium [L(3)Re(CO)(3)](+)[ReCO)(5)](-) (2) silylene complexes were prepared in one pot syntheses by reacting 1 equivalent of Mn(2)(CO)(10) with 2 equivalents of stable N-heterocyclic chlorosilylene L {L = PhC(NtBu)(2)SiCl} and 1 equivalent of Re(2)(CO)(10) with 3 equivalents of L in toluene at room temperature. Both complexes 1 and 2 were characterized by single-crystal X-ray structural analysis, NMR and IR spectroscopy, EI-MS spectrometry, and elemental analysis.