TY - JOUR
T1 - Bis(phosphinimino)methanides as ligands in divalent lanthanide and alkaline earth chemistry - Synthesis, structure, and catalysis
AU - Panda, Tarun K.
AU - Zulys, Agustino
AU - Gamer, Michael T.
AU - Roesky, Peter W.
N1 - Funding Information:
This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie.
PY - 2005/11/15
Y1 - 2005/11/15
N2 - Divalent bis(phosphinimino)methanide lanthanide complexes of composition [{(Me3SiNPPh2)2CH}EuI(THF)]2 and [{(Me3SiNPPh2)2CH}YbI(THF)2] have been prepared by a salt metathesis reactions of K{CH(PPh2NSiMe 3)2} and LnI2. Further reactions of these complexes with [K(THF)nN(PPh2)2] led selectively to the heteroleptic amido complexes [{(Me3SiNPPh 2)2CH}Ln{(Ph2P)2N}(THF)] (Ln = Eu, Yb). The ytterbium complex can also be obtained by reduction of [{CH(PPh 2NSiMe3)2}Yb{(Ph2P)2N}Cl] with elemental potassium. The single crystals of [{(Me3SiNPPh 2)2CH}Ln{(Ph2P)2N}(THF)] contain enantiomerically pure complexes. As a result of the similar ionic radii of the divalent lanthanides and the heavier alkaline earth metals some similarities in coordination chemistry of the bis(phosphinimino)methanide ligand were anticipated. Therefore, MI2 (M = Ca, Sr, Ba) was reacted with K{CH(PPh2NSiMe3)2} to give [{(Me 3SiNPPh2)2CH}CaI(THF)2], [{(Me 3SiNPPh2)2CH}SrI(THF)]2, and [{(Me3SiNPPh2)2CH}BaI(THF)2] 2, respectively. As expected the Sr and Eu complexes and the Ca and Yb complexes are very similar, whereas for the Ba compound, as a result of the large ion radius, a different coordination sphere is observed. For all new complexes the solid-state structures were established by single crystal X-ray diffraction. In the solid-state the {CH(PPh2NSiMe3) 2}- ligand acts as tridentate donor forming a long methanide carbon metal bond. Thus, all complexes presented can be considered as organometallic compounds. [{(Me3SiNPPh2) 2CH}YbI(THF)2] was also used as precatalyst for the intramolecular hydroamination/cyclization reaction of different aminoalkynes and aminoolefines. Good yields but moderate activities were observed.
AB - Divalent bis(phosphinimino)methanide lanthanide complexes of composition [{(Me3SiNPPh2)2CH}EuI(THF)]2 and [{(Me3SiNPPh2)2CH}YbI(THF)2] have been prepared by a salt metathesis reactions of K{CH(PPh2NSiMe 3)2} and LnI2. Further reactions of these complexes with [K(THF)nN(PPh2)2] led selectively to the heteroleptic amido complexes [{(Me3SiNPPh 2)2CH}Ln{(Ph2P)2N}(THF)] (Ln = Eu, Yb). The ytterbium complex can also be obtained by reduction of [{CH(PPh 2NSiMe3)2}Yb{(Ph2P)2N}Cl] with elemental potassium. The single crystals of [{(Me3SiNPPh 2)2CH}Ln{(Ph2P)2N}(THF)] contain enantiomerically pure complexes. As a result of the similar ionic radii of the divalent lanthanides and the heavier alkaline earth metals some similarities in coordination chemistry of the bis(phosphinimino)methanide ligand were anticipated. Therefore, MI2 (M = Ca, Sr, Ba) was reacted with K{CH(PPh2NSiMe3)2} to give [{(Me 3SiNPPh2)2CH}CaI(THF)2], [{(Me 3SiNPPh2)2CH}SrI(THF)]2, and [{(Me3SiNPPh2)2CH}BaI(THF)2] 2, respectively. As expected the Sr and Eu complexes and the Ca and Yb complexes are very similar, whereas for the Ba compound, as a result of the large ion radius, a different coordination sphere is observed. For all new complexes the solid-state structures were established by single crystal X-ray diffraction. In the solid-state the {CH(PPh2NSiMe3) 2}- ligand acts as tridentate donor forming a long methanide carbon metal bond. Thus, all complexes presented can be considered as organometallic compounds. [{(Me3SiNPPh2) 2CH}YbI(THF)2] was also used as precatalyst for the intramolecular hydroamination/cyclization reaction of different aminoalkynes and aminoolefines. Good yields but moderate activities were observed.
KW - Alkaline earth metals
KW - Bis(phosphinimino)methanides
KW - Catalysis
KW - Hydroamination
KW - Lanthanides
KW - P,N ligands
UR - http://www.scopus.com/inward/record.url?scp=27644553070&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2005.03.023
DO - 10.1016/j.jorganchem.2005.03.023
M3 - Article
AN - SCOPUS:27644553070
SN - 0022-328X
VL - 690
SP - 5078
EP - 5089
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 23
ER -