Lanthanide versus actinide reactivity in the formation of sterically crowded [(C(5)Me(5))(3)ML(n)] nitrile and isocyanide complexes

Chemistry : a European Journal
William J EvansJoseph W Ziller

Abstract

The limits of steric crowding in organometallic metallocene complexes have been examined by studying the synthesis of [(C(5)Me(5))(3)ML(n)] complexes as a function of metal in which L=Me(3)CCN, Me(3)CNC, and Me(3)SiCN. The bis(tert-butyl nitrile) complexes [(C(5)Me(5))(3)Ln(NCCMe(3))(2)] (Ln=La, 1; Ce, 2; Pr, 3) can be isolated with the largest lanthanide metal ions, La(3+), Ce(3+), and Pr(3+). The Pr(3+) ion also forms an isolable mono-nitrile complex, [(C(5)Me(5))(3)Pr(NCCMe(3))] (4), whereas for Nd(3+) only the mono-adduct [(C(5)Me(5))(3)Nd(NCCMe(3))] (5) was observed. With smaller metal ions, Sm(3+) and Y(3+), insertion of Me(3)CCN into the M--C(C(5)Me(5)) bond was observed to form the cyclopentadiene-substituted ketimide complexes [(C(5)Me(5))(2)Ln{NC(C(5)Me(5))(CMe(3))}(NCCMe(3))] (Ln=Sm, 6; Y, 7). With tert-butyl isocyanide ligands, a bis-isocyanide product can be isolated with lanthanum, [(C(5)Me(5))(3)La(CNCMe(3))(2)] (8), and a mono-isocyanide product with neodymium, [(C(5)Me(5))(3)Nd(CNCMe(3))] (9). Silicon-carbon bond cleavage was observed in reactions between [(C(5)Me(5))(3)Ln] complexes and trimethylsilyl cyanide, Me(3)SiCN, to produce the trimeric cyanide complexes [{(C(5)Me(5))(2)Ln(mu-CN)(NCSiMe(3))}(3)] (Ln=La...Continue Reading

References

Jun 13, 2002·Chemical Reviews·William J Evans, Benjamin L Davis
Nov 20, 2003·Journal of the American Chemical Society·William J EvansJoseph W Ziller
Jul 15, 2004·Dalton Transactions : an International Journal of Inorganic Chemistry·Thouraya MehdouiMichel Ephritikhine
Oct 26, 2005·Inorganic Chemistry·William J EvansJoseph W Ziller
Aug 16, 2006·Proceedings of the National Academy of Sciences of the United States of America·William J EvansJoseph W Ziller
Jun 14, 1999·Angewandte Chemie·William J EvansJoseph W Ziller

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Citations

May 30, 2017·Chemical Science·Michał S DutkiewiczPolly L Arnold
Mar 27, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Jean-Claude BerthetMichel Ephritikhine
Jun 6, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Pokpong RungthanaphatsophonJustin R Walensky
May 14, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Thomas J MuellerWilliam J Evans
Aug 20, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Michael A BoreenJohn Arnold
Jun 17, 2015·Angewandte Chemie·Stephen T Liddle
Mar 31, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Wenshan RenMarc D Walter
Jan 18, 2018·Chemical Communications : Chem Comm·S S RudelF Kraus
Jun 17, 2014·Inorganic Chemistry·Alexandre HervéMichel Ephritikhine
Aug 18, 2021·Chemistry : a European Journal·Michael L TarltonJustin R Walensky

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