TY - JOUR
T1 - Bis(phosphinimino)methanide rare earth amides
T2 - Synthesis, structure, and catalysis of hydroamination/cyclization, hydrosilylation, and sequential hydroamination/hydrosilylation
AU - Rastätter, Marcus
AU - Agustino, null
AU - Roesky, Peter W.
PY - 2007
Y1 - 2007
N2 - A series of yttrium and lanthanide amido complexes [Ln{N-(SiHMe 2)2}2{CH(PPh2NSiMe3) 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(PPh2NSiMe3)2] or from KN-(SiHMe2)2 and [Ln(CH(PPh2NSiMe 3)2}-Cl2]2, while in a third approach the lanthanum compound was synthesized in a one-pot reaction starting from K{CH(PPh2NSiMe3)2}, LaCl3, and KN-(SiHMe2)2. All the complexes have been characterized by single-crystal X-ray diffraction. The new complexes, [Ln{N(SiHMe 2)2}2{CH(PPh2NSiMe3) 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.
AB - A series of yttrium and lanthanide amido complexes [Ln{N-(SiHMe 2)2}2{CH(PPh2NSiMe3) 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(PPh2NSiMe3)2] or from KN-(SiHMe2)2 and [Ln(CH(PPh2NSiMe 3)2}-Cl2]2, while in a third approach the lanthanum compound was synthesized in a one-pot reaction starting from K{CH(PPh2NSiMe3)2}, LaCl3, and KN-(SiHMe2)2. All the complexes have been characterized by single-crystal X-ray diffraction. The new complexes, [Ln{N(SiHMe 2)2}2{CH(PPh2NSiMe3) 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.
KW - Catalysis
KW - Hydroamination
KW - Hydrosilylation
KW - N,P ligands
KW - Rare earth metals
UR - http://www.scopus.com/inward/record.url?scp=34250303382&partnerID=8YFLogxK
U2 - 10.1002/chem.200601510
DO - 10.1002/chem.200601510
M3 - Article
C2 - 17373002
AN - SCOPUS:34250303382
SN - 0947-6539
VL - 13
SP - 3606
EP - 3616
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 13
ER -