Transamination of KN(SiMe3)(2) with 2,6-diisopropylphenylamine (2,6-diisopropylaniline) in toluene at ambient temperature yields [K{N(H)-Dipp}center dot KN(SiMe3)(2)] (1) regardless of the applied stoichiometry. Recrystallization of 1 in the presence of tetramethylethylenediamine (TMEDA) and tetrahydrofuran (THF) leads to the formation of [(mu-thf)K-2{N(H)Dipp}(2)](infinity) (2), whereas potassium bis(trimethylsilyl)amide remains in solution. Addition of pentamethyldiethylenetriamine (PMDETA) gives [(pmdeta)KIN(H)Dipp}](2) (3). In contrast to the thf and pmdeta adducts, which lead to dissociation of 1 into homoleptic species, addition of bidentate dimethoxyethane maintains the mixed complex [(dme)K{mu-N(SiMe3)(2)}{mu-N(H)Dipp}K](2) (4). A complete transamination of 2,6-diisopropylaniline with KN(SiMe3)(2) in toluene at 100 degrees C yields {K{N(H)Dipp}] (5), which reacts with CaI2 to give [(thf)(n)Ca{N(H)Dipp}(2)] (6), [(pmdeta)Ca{N(H)Dipp}(2)] (7), and [(dme)(2)Ca{N(H)Dipp}(2)] (8), depending on the solvents and coligands. Excess potassium 2,6-diisopropylphenylamide allows the formation of the calciate [K2Ca{N(H)Dipp}(4)](infinity) (9). Hydroamination of diphenylbutadiyne with 2,6-diisopropylaniline in the presence of catalytic amounts of 9 gives tetracyclic 2,6-diisopropyl-9,11,14,15-tetraphenyl-8-azatetracyclo[8.5.0.0(1,7).0(2,13)]pentadeca-3,5,7,9,11,14-hexaene (10). Solid-state structures are reported for 2-4 and 7-10. Compound 10 slowly rearranges to tetracyclic 5a,9-diisopropyl-2,3,10,11-tetraphenyl-5a,6-dihydro-2a(1),6-ethenocyclohepta[cd]isoindole (11), which is slightly favored according to quantum chemical studies.
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