Monomeric Rare-Earth Metal Silyl-Thiophosphinoyl-Alkylidene Complexes: Synthesis, Structure, and Reactivity

Chemistry : a European Journal
Chen WangYaofeng Chen

Abstract

A series of monomeric rare-earth metal silyl-thiophosphinoyl-alkylidene complexes [LLn{C(SiR3 )PPh2 S}] (5: Ln=Lu, R=Me; 6: Ln=Lu, R=Ph; 7: Ln=Y, R=Me; 8: Ln=Y, R=Ph; 9: Ln=Sm, R=Ph; 10: Ln=Sm, R=Me; 11: Ln=La, R=Ph; L=[MeC(NDIPP)CHC(Me)(NCH2 CH2 N(Me)2 )]- , DIPP=2,6-(iPr)2 C6 H3 ) have been synthesized and structurally characterized. The influences of rare-earth metal ions, ancillary ligands, and alkylidene groups on the reactivity of complexes 5-11 and the related scandium complexes [LSc{C(SiR3 )PPh2 S}] (1: R=Me; 2: R=Ph) and [L'Sc{C(SiR3 )PPh2 S}] (3: R=Me; 4: R=Ph; L'=[MeC(NDIPP)CHC(Me)(NCH2 CH2 N(iPr)2 )]- ) have been studied. Reactions of these rare-earth metal alkylidene complexes with PhCN give four kinds of products, the formation of which is dependent on the rare-earth metal ions, ancillary ligands, and alkylidene groups of the complexes. In the reactions with tBuNC, unusual C-P bond cleavage of the alkylidene group and C≡C triple bond formation occur. Complexes 10 and 11 also react with PhSiH3 to form hydrides, which subsequently undergo Ln-H addition to the C=N bond of the ancillary ligand L. DFT calculations have been used to analyze the bonding in complex 10, which exhibits a polarized three centers Sm-C-P π int...Continue Reading

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Nov 28, 2017·Journal of the American Chemical Society·Weiqing MaoYaofeng Chen

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Citations

Oct 18, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Wei SuCongqing Zhu
Jun 8, 2021·Chemical Communications : Chem Comm·Peng DengJianhua Cheng
Jun 14, 2019·Chemical Reviews·Marie Fustier-BoutignonNicolas Mézailles

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