Issue 21, 2024

Tuning the reactivity of an yttrium complex bearing a functionalized silylamido ligand using solvated KCl

Abstract

Distinguished functionalization of the silyl-bridged amido PhSiH2-substituted alkyl ligand in an yttrium complex under solvated KCl additive conditions is described. Treatment of the TpMe2-supported yttrium silyl-bridged amido PhSiH2-substituted alkyl complex 1 (TpMe2Y[η2-(C,N)-CH(SiH2Ph)Si(Me2)NSiMe3]) with elemental sulfur S8 under KCl additive conditions afforded three structurally characterized yttrium complexes (TpMe2)3Y43–η122-(S3)SiPh]2(μ–η22-S2)(μ-Cl)(THF) (2), [(TpMe2)2Y]22+{(TpMe2Y)33–η123-(S3)SiPh]3K(THF)}2− (3), and [(TpMe2)2Y]+{[TpMe2Y(ClN(SiMe3)2)2]μ-(Cl)2K} (4), providing a straightforward method for construction of phenylsilyl trisulfide PhSiS33− under mild conditions. Without KCl, 1 reacted with S8 to give a routine Y–C insertion product 5 (TpMe2Y[η2-(S,N)-SCH(SiH2Ph)Si(Me2)NSiMe3]). Similarly, the reaction of 1 with isothiocyanate under KCl additive conditions formed a double insertion product (TpMe2)2Y2{μ–η32-(S,S,N,N,N)-N(SiMe3)Si(Me2)CH[C(S) = NC6H4CH3-p]2}Cl (7), accompanied by the elimination of an intermolecular silyl-migration product KNSiMe3Si(Me2)CH(SiH2Ph)2 (I). The intermolecular silyl migration was also observed in the three-component reaction of 1 with tBuNC, and CO2. The reaction of 1 and PhNCS without KCl additive only produced 8 (TpMe2Y[η2-(S,N)-SC(N(SiH2Ph)Ph) = CHSi(Me2)NSiMe3]). These results indicate that the possible weak interaction between a rare-earth ion and KCl might play a crucial role in the conversion of this modified silylamino ligand.

Graphical abstract: Tuning the reactivity of an yttrium complex bearing a functionalized silylamido ligand using solvated KCl

Supplementary files

Article information

Article type
Research Article
Submitted
26 Jul 2024
Accepted
07 Sep 2024
First published
14 Sep 2024

Inorg. Chem. Front., 2024,11, 7501-7511

Tuning the reactivity of an yttrium complex bearing a functionalized silylamido ligand using solvated KCl

Q. You, J. Cai, J. Zhang and X. Zhou, Inorg. Chem. Front., 2024, 11, 7501 DOI: 10.1039/D4QI01882F

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