Alkali metal complexes of an enantiopure iminophosphonamide bearing chiral centers at both nitrogen atoms are described. They show bright phosphorescence and thermally activated delayed fluorescence (TADF).
Selective substitution and insertion reactions of silylenes into the cyclo-P 5 ring of [Cp*Fe(η 5 -P 5 )] are reported. The selective substitution of one P atom by an isoelectronic [LSi] fragment (L = PhC(N t Bu) 2 ) leads to [(η 4 -P 4 SiL)FeCp*] and [LSi(Cl)P-SiL(Cl) 2 ]. To elucidate the reaction mechanism, [{LSi(N(SiMe 3 ) 2 )}{(η 4 -P 5 )FeCp*}], in which the silicon atom binds to the cyclo-P 5 ring, was synthesized as a model compound for the reaction intermediate. The insertion of [LSi-SiL] into the cyclo-P 5 ring of [Cp*Fe(η 5 -P 5 )] resulted in [{η 4 -P 5 (SiL) 2 }FeCp*] featuring a cyclo-P 5 (SiL) 2 ring, which corresponds to the largest silicon−polyphosphorus ring known in a complex.
Pentaphosphaferrocene, [Cp*Fe(η5-P5)], was used as an air-stable source of polyphosphorus units to synthesize a novel bis(germylene)-functionalized transition metal polyphosphide complex, which further undergoes a unique constitutional isomerization.
The synthesis of calcium complexes ligated by three different chiral iminophosphonamide ligands, L‐H (L=[Ph2P{N(R)CH(CH3)Ph}2]), L′‐H (L′=[Ph2P{NDipp}{N(R)CH(CH3)Ph}]), (Dipp=2,6‐iPr2C6H3), and L′′‐H (L′′=[Ph2P{N(R)CH(CH3)naph}2]), (naph=naphthyl) is presented. The resulting structures [L2Ca], [L′2Ca], and [L′′2Ca] represent the first examples of enantiopure homoleptic calcium complexes based on this type of ligands. The calcium complexes show blue–green photoluminescence (PL) in the solid state, which is especially bright at low temperatures. Whereas the emission of [L′′2Ca] is assigned to the fluorescence of naphthyl groups, the PL of [L2Ca] and [L′2Ca] is contributed by long‐lived phosphorescence and thermally activated delayed fluorescence (TADF), with a strong variation of the PL lifetimes over the temperature range of 5–295 K. Furthermore, an excellent catalytic activity was found for these complexes in hydroboration of ketones at room temperature, although no enantioselectivity was achieved.
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