2020
DOI: 10.1002/chem.202001207
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Modification of Yttrium Silyl‐Bridged Amide Alkyl Complexes through Si−H/C−H Cross‐Dehydrocoupling of Silanes with a Silylamino Ligand: Synthesis, Reactivity, and Mechanism

Abstract: A new method for the modification of a silylamino ligand has been developed through mono and dual C(sp3)−H/Si−H cross‐dehydrocoupling with silanes. The reaction of [LY{η2‐(C,N)‐CH2Si(Me2)NSiMe3}] (L=bis(2,6‐diisopropylphenyl)‐β‐diketiminato, L′ (1L′); L=tris(3,5‐dimethylpyrazolyl)borate, TpMe2 (1TpMe2)) with 2 equivalents of PhSiH3 in toluene gave the complexes [LY{η2‐(C,N)‐C(SiH2Ph)2Si(Me2)NSiMe3}] (L=L′ (2L’); L=TpMe2 (2TpMe2)). Moreover, 1TpMe2 reacted with the secondary silanes Ph2SiH2 and Et2SiH2 to affor… Show more

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Cited by 2 publications
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“…The 1 H NMR spectrum of 2 displays a new singlet peak at δ = 4.99 ppm, which is attributed to the resonance of the OCC H fragment in the newly formed silyl-bridged amido formyl ligand OCCH(SiH 2 Ph)SiMe 2 NSiMe 3 , and is significantly different from that of the corresponding C H moiety ( δ = −0.16 ppm) in 1 . 19 The latter is a typical C–H resonance of the alkyl ligand bonded to Y metal. Moreover, the 13 C NMR spectrum of 2 also displays two new singlet peaks at δ = 196.6 ppm (–CH C –O) and at δ = 90.9 ppm ( C HC–O), which are attributable to the resonances of the OCCH moiety.…”
Section: Resultsmentioning
confidence: 99%
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“…The 1 H NMR spectrum of 2 displays a new singlet peak at δ = 4.99 ppm, which is attributed to the resonance of the OCC H fragment in the newly formed silyl-bridged amido formyl ligand OCCH(SiH 2 Ph)SiMe 2 NSiMe 3 , and is significantly different from that of the corresponding C H moiety ( δ = −0.16 ppm) in 1 . 19 The latter is a typical C–H resonance of the alkyl ligand bonded to Y metal. Moreover, the 13 C NMR spectrum of 2 also displays two new singlet peaks at δ = 196.6 ppm (–CH C –O) and at δ = 90.9 ppm ( C HC–O), which are attributable to the resonances of the OCCH moiety.…”
Section: Resultsmentioning
confidence: 99%
“…Complex 1 was prepared according to a literature procedure. 19 Synthesis and characterization of complexes 2-6 Synthesis and characterization of complex Tp Me2 Y[κ 2 -(C,N)-CH(SiH 2 Ph)SiMe 2 NSiMe 3 ](THF) (2). Dry CO gas (1 atm) was added to a toluene (10 mL) solution of 1 (0.5 mmol, 0.36 g) at room temperature and then the mixture was heated to 50 °C and stirred for 6 h (Scheme S1 †).…”
Section: Methodsmentioning
confidence: 99%
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