ABSTRACT
A series of 2,1,3-benzothiadiazole-Au(I)-L complexes have been synthesised, structurally characterised and investigated for their photophysical properties. These are the first organometallic Au(I) complexes containing a C-Au bond on the highly electron-deficient benzothiadiazole unit. The complexes exhibit solution-phase phosphorescence at room temperature, assigned to the intrinsic triplet state of the benzothiadiazole unit that is efficently populated through its attachment to gold. Comparison with routinely reported Au(I) complexes, which include intervening alkenyl linkers, suggests that previous assignments of their phosphorescence as 1π â π*(CîCR) might be incomplete. Our observations affirm that, in addition to the heavy atom effect, breaking symmetry in the involved aryl motif may be of importance in controlling the luminescence properties.
ABSTRACT
Hybrid Density Functional Theory (DFT) calculations for multiple conformers of the insertion reactions of a methylenecyclopropane into the Ti-C bond of two differently α-substituted titanaaziridines explain the experimentally observed differences in regioselectivity between catalytic hydroaminoalkylation reactions of methylenecyclopropanes with α-phenyl-substituted secondary amines and corresponding stoichiometric reactions of a methylenecyclopropane with titanaaziridines, which can only be achieved with α-unsubstituted titanaaziridines. In addition, the lack of reactivity of α-phenyl-substituted titanaaziridines as well as the diastereoselectivity of the catalytic and stoichiometric reactions can be understood.
ABSTRACT
Intermolecular hydroaminoalkylation reactions of symmetrical and unsymmetrical alkynes with tertiary amines take place in the presence of catalytic amounts of TiBn4 , Ph3 C[B(C6 F5 )4 ], and a sterically demanding aminopyridinato ligand precursor. The resulting products, synthetically and pharmaceutically useful tertiary ß,γ-disubstituted allylic amines, are formed in convincing yields and with excellent stereoselectivity. Particularly promising for future applications is the fact that even the industrial side product trimethylamine can be used as a substrate.
ABSTRACT
Intermolecular hydroaminoalkylation reactions of alkynes with secondary amines, which selectively give access to allylic amines with E configuration of the alkene unit, are achieved in the presence of titanium catalysts. Successful reactions of symmetrically substituted diaryl- and dialkylalkynes as well as a terminal alkyne take place with N-benzylanilines, N-alkylanilines, and N-alkylbenzylamines.
ABSTRACT
Intermolecular hydroaminoalkylation reactions of propadiene with selected secondary amines take place in the presence of a 2,6-bis(phenylamino)pyridinato titanium catalyst. The corresponding products, synthetically useful allylamines, are formed in convincing yields and with high selectivities. In addition, propadiene easily inserts into the titanium-carbon bond of a titanaaziridine.