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

Autor: Yan Yang, Laurent Maron, Li Xiang, Yaofeng Chen, Weiqing Mao, Xuebing Leng, Jian Fang, Chen Wang
Přispěvatelé: Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences [Beijing] (CAS), Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou University, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), National Natural Science Foundation of China [21732007, 21325210], Strategic Priority Research Program of the Chinese Academy of Sciences [XDB20000000], Program of Shanghai Academic Research Leader [18XD1404900], HPCs CALcul en Midi-Pyrenees (CALMIP-EOS grant) [1415]
Rok vydání: 2018
Předmět:
Zdroj: Chemistry-A European Journal
Chemistry-A European Journal, 2018, 24 (52), pp.13903-13917. ⟨10.1002/chem.201802791⟩
ISSN: 0947-6539
1521-3765
DOI: 10.1002/chem.201802791
Popis: International audience; A series of monomeric rare-earth metal silyl-thiophosphinoyl-alkylidene complexes [LLn{C(SiR3)PPh2S}] (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)(NCH2CH2N(Me)(2))](-), DIPP=2,6-(iPr)(2)C6H3) 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)PPh2S}] (1: R=Me; 2: R=Ph) and [LSc{C(SiR3)PPh2S}] (3: R=Me; 4: R=Ph; L=[MeC(NDIPP)CHC(Me)(NCH2CH2N(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 CC 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 interaction, and to rationalize the reactivity by computing reaction mechanisms. The difference in reactivity of PhCN and tBuNC is due to the electron density delocalization that is enabled by the phenyl group rather than the tBu group.
Databáze: OpenAIRE
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