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A series of compressed M[Li313Ti2] (M = Li, Na, K, Rb, Cs) and expanded helicates M4[13Ti2] has been obtained. The helicates Li3[M13Ti2] or M4[13Ti2] with M = Na+, K+, Rb+, or Cs+ adopt the expanded structure in solution. By crystallization the compressed structures M[Li313Ti2] (M = Na, Rb) are obtained. This represents an example of cation-translocation based isomerism. [ABSTRACT FROM AUTHOR]

Facile α‐H elimination from tetrakis(trimethylsilylmethyl)titanium precursors to give adducts of (alkylidene)bis(alkyl)titanium complexes is induced by light alkali metal amides of the NNNN‐type macrocyclic anionic ligand Me3TACD [(Me3TACD)H=1,4,7‐trimethyl‐1,4,7,10‐tetraazacyclododecane]. In the crystal, the alkali metal interacts with the carbene carbon atom or with the CH2 group of the trimethylsilymethyl ligand. The nucleophilic character of the carbene carbon atom was shown by the reaction with benzophenone and terminal acetylenes. Facile α‐H elimination from tetrakis(trimethylsilylmethyl)titanium is induced by alkali metal amides to give adducts of (alkylidene)bis(alkyl)titanium complexes. In the crystal, the alkali metal interacts with the carbene carbon atom or with the CH2 group of the trimethylsilymethyl ligand. The nucleophilic character of the carbene carbon atom was shown by reactions with benzophenone and terminal acetylenes. [ABSTRACT FROM AUTHOR]

A series of light alkali metal organoperoxides [MOOR] (M=Li, Na, K; R= tBu, CMe2Ph) were isolated in mononuclear form, aided by the tetradentate and neutral NNNN-type macrocycle Me4TACD (L; Me4[12]aneN4=1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane) and strong hydrogen bonds from additional ROOH molecules. The Na and K compounds are characterized by short O−H⋅⋅⋅O contacts, in the case of the Na derivative as short as 2.41 Å. [ABSTRACT FROM AUTHOR]