Bis(phosphinimino)methanide rare earth amides: synthesis, structure, and catalysis of hydroamination/cyclization, hydrosilylation, and sequential hydroamination/hydrosilylation.
A series of yttrium and lanthanide amido complexes [Ln{N(SiHMe(2))2}2{CH(PPh(2)NSiMe(3))2}] (Ln=Y, La, Sm, Ho, Lu) were synthesized by three different pathways. The title compounds can be obtained either from [Ln{N(SiHMe(2))2}3(thf)2] and [CH(2)(PPh(2)NSiMe(3))2] or from KN(SiHMe(2))2 and [Ln{CH(PPh(2)NSiMe(3))2}Cl(2)]2, while in a third approach the lanthanum compound was synthesized in a one-pot reaction starting from K{CH(PPh(2)NSiMe(3))2}, LaCl3, and KN(SiHMe(2))2. All the complexes have been characterized by single-crystal X-ray diffraction. The new complexes, [Ln{N(SiHMe(2))2}2{CH(PPh(2)NSiMe(3))2}], were used as catalysts for hydroamination/cyclization and hydrosilylation reactions. A clear dependence of the reaction rate on the ionic radius of the center metal was observed, showing the lanthanum compound to be the most active one in both reactions. Furthermore, a combination of both reactions--a sequential hydroamination/hydrosilylation reaction--was also investigated.
Rastätter
Marcus
M
Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstrasse 34-36, 14195 Berlin, Germany.
Zulys
Agustino
A
Roesky
Peter W
PW
D000577:Amides / Q000737:chemistry* / Q000378:metabolism; D000586:Amination; D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D007477:Ions; D008674:Metals, Rare Earth / Q000737:chemistry* / Q000378:metabolism; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010316:Particle Size; D012821:Silanes / Q000737:chemistry*
D000577:Amides; D007477:Ions; D008674:Metals, Rare Earth; D009942:Organometallic Compounds; D012821:Silanes