Abstract:The application of C[1]magnesocenophanes in dehydrocoupling catalysis is reported. Two new cycloalkylidenebridged C[1]magnesocenophanes were synthesized and structurally characterized. These C[1]magnesocenophanes were used as catalysts in amine−borane dehydrocoupling and, more extensively, in amine−silane cross-dehydrocoupling. The substrate scope, involving different aliphatic, aromatic, and benzylic amines, was probed and the mechanism of this cross-dehydrocoupling catalysis was investigated.
“…Literature known ansa-half-sandwich ligands [50][51][52][53] were reacted with dibutylmagnesium to obtain the corresponding ansa-halfsandwich magnesium complexes 1 a-d (Scheme 1). Similar to magnesocenophanes, [24,25,[54][55][56] 1 a-d possess Lewis acidic magnesium atoms and crystalized as solvent adducts from donor solvent (Figure 1, S14-S18). In case of 1 a-c, mono dme adducts are observed in the solid state, with the dme molecule coordinated to the magnesium atom via both oxygen atoms and the magnesium atom exhibiting an η 5 coordination mode to the Cp group.…”
Section: Synthesis and Characterization Of Ansa-half-sandwich Magnesi...mentioning
confidence: 99%
“…Recently, we demonstrated that [1]magnesocenophanes are potent catalysts in the dehydrocoupling of amine-boranes. [24,25] While many magnesium based catalysts require elevated temperatures to operate, [26][27][28][29] [1]magnesocenophanes were able to catalyze the dehydrocoupling reactions of different dialkylamine-boranes at room temperature. [24,25] We therefore started our investigations into the catalytic abilities of ansa-halfsandwich magnesium complexes 1 a-d by testing their performance in the dehydrocoupling of amine-boranes.…”
The synthesis, characterization and catalytic application of a series of constrained geometry ansa‐half‐sandwich complexes of magnesium is reported. These versatile s‐block catalysts were applied in different dehydrocoupling and hydroelementation reactions, demonstrating a broad applicability with particularly remarkable performance in dehydrocoupling reactions.
“…Literature known ansa-half-sandwich ligands [50][51][52][53] were reacted with dibutylmagnesium to obtain the corresponding ansa-halfsandwich magnesium complexes 1 a-d (Scheme 1). Similar to magnesocenophanes, [24,25,[54][55][56] 1 a-d possess Lewis acidic magnesium atoms and crystalized as solvent adducts from donor solvent (Figure 1, S14-S18). In case of 1 a-c, mono dme adducts are observed in the solid state, with the dme molecule coordinated to the magnesium atom via both oxygen atoms and the magnesium atom exhibiting an η 5 coordination mode to the Cp group.…”
Section: Synthesis and Characterization Of Ansa-half-sandwich Magnesi...mentioning
confidence: 99%
“…Recently, we demonstrated that [1]magnesocenophanes are potent catalysts in the dehydrocoupling of amine-boranes. [24,25] While many magnesium based catalysts require elevated temperatures to operate, [26][27][28][29] [1]magnesocenophanes were able to catalyze the dehydrocoupling reactions of different dialkylamine-boranes at room temperature. [24,25] We therefore started our investigations into the catalytic abilities of ansa-halfsandwich magnesium complexes 1 a-d by testing their performance in the dehydrocoupling of amine-boranes.…”
The synthesis, characterization and catalytic application of a series of constrained geometry ansa‐half‐sandwich complexes of magnesium is reported. These versatile s‐block catalysts were applied in different dehydrocoupling and hydroelementation reactions, demonstrating a broad applicability with particularly remarkable performance in dehydrocoupling reactions.
“…In 2021, the Scha ¨fer group reported the first example of C [1]magnesocenophanes for the dehydrogenative coupling of amines with silanes. 37 There was limited reactivity with this catalytic system and better conversions and selectivity were obtained when amine was coupled with diphenylsilane as compared to phenylsilane.…”
Section: Alkali and Alkaline Earth Metalsmentioning
Efficient catalytic routes to prepare electronically and sterically distinct silylamine building blocks for the step-economic synthesis of amines and N-heterocycles.
“…The dehydrocoupling between amines and hydrosilanes seems to be the most attractive route, due to the formation of H 2 as the by-product (Figure 1, c). [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] Unfortunately, this approach is completely impractical for the preparation of a highly important trimethylsilyl-protecting group, due to the pyrophoricity of gaseous Me 3 SiH. Moreover, the control of the chemoselectivity for Si-H/N-H dehydrocoupling has proved to be challenging due to the possible formation of several products including polymeric silazanes and a mixture of mono-and di-silylated amines.…”
mentioning
confidence: 99%
“…1c). [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] Unfortunately, this approach is completely impractical for the preparation of a highly important trimethylsilyl-protecting group, due to the pyrophoricity of gaseous Me 3 SiH. Moreover, the control of the chemoselectivity for Si-H/N-H dehydrocoupling has proved to be challenging due to the possible formation of several products including polymeric silazanes and a mixture of mono-and disilylated amines.…”
The catalytic synthesis of silylamines mediated by s- and p-block catalysts is largely underdeveloped. Herein, commercially available potassium bis(trimethylsilyl)amide serves as an efficient alternative to transition metal complexes. N–H/Si–C dealkynative...
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