TY - JOUR
T1 - Phosphinomethanid-komplexe der lanthanoide
AU - Karsch, Hans H.
AU - Ferazin, Gunter
AU - Kooijman, Huub
AU - Steigelmann, Oliver
AU - Schier, Annette
AU - Bissinger, Peter
AU - Hiller, Wolfgang
PY - 1994/11/29
Y1 - 1994/11/29
N2 - By reaction of LnI2 · 2THF, Ln Yb, Sm with the phosphinomethanides Li[C(PMe2)2X], X SiMe3, PMe2 the addition products {(THF)Ln[C(PMe2)2X]2I2Li(THF)}, Ln Yb, X SiMe3 (1a), X PMe2 (1b) and Ln Sm, X SiMe3 (2) are obtained; 1a could be characterized by X-ray crystal structure analysis. In contrast complete substitution is achieved in the reaction of lanthanide triflates with lithium phosphinomethanides. Thus the seven-coordinated and X-ray structurally characterized complex {(THF)Lu[C(PMe2)2(SiMe3)]3} (3) is obtained. Lu[C(PMe2)2(SiMe3)]3 (4) could be obtained from 3 by removing thf in vacuo or by reaction of Lu(CF3SO3)3 with Li[C(PMe2)2(SiMe3)] in toluene. The derivative {(THF)Lu(Me)[C(PMe2)2(SiMe3)]2} (5) has been isolated by treatment of 3 with LiMe. In a somewhat random way, one run with LiMe gave the X-ray structurally characterized, anionic complex [(THF)4Li]{Lu(OSiMe3)[CPMe2)2(SiMe3)]3} (6) obviously by cleavage of silicon grease. A coordination number of eight is observed in the anionic complexes {Ln[C(PMe2) 2(SiMe3)]4Li}, Ln Er (7), Y (8) und La (9). The X-ray crystal structure of 9 verifies the new type of an eightfold phosphorus coordinated lanthanoid center. In compounds Sc[C(PMe2) 2X)]3, X SiMe3 (10a) and X PMe2 (10b) the phosphino-methanide ligands are arranged in an intermediate coordination mode between σ-chelating and π-type coordination as revealed by X-ray diffraction. The X-ray structurally characterized dimeric complex {Sm[CH(PMe2)2]3} 2 (11) combines two different phosphinomethanide coordination modes. Two phosphinomethanide ligands in 11) adopt a π-type coordination, the third ligand is arranged in a η2, μ-C,P fashion.
AB - By reaction of LnI2 · 2THF, Ln Yb, Sm with the phosphinomethanides Li[C(PMe2)2X], X SiMe3, PMe2 the addition products {(THF)Ln[C(PMe2)2X]2I2Li(THF)}, Ln Yb, X SiMe3 (1a), X PMe2 (1b) and Ln Sm, X SiMe3 (2) are obtained; 1a could be characterized by X-ray crystal structure analysis. In contrast complete substitution is achieved in the reaction of lanthanide triflates with lithium phosphinomethanides. Thus the seven-coordinated and X-ray structurally characterized complex {(THF)Lu[C(PMe2)2(SiMe3)]3} (3) is obtained. Lu[C(PMe2)2(SiMe3)]3 (4) could be obtained from 3 by removing thf in vacuo or by reaction of Lu(CF3SO3)3 with Li[C(PMe2)2(SiMe3)] in toluene. The derivative {(THF)Lu(Me)[C(PMe2)2(SiMe3)]2} (5) has been isolated by treatment of 3 with LiMe. In a somewhat random way, one run with LiMe gave the X-ray structurally characterized, anionic complex [(THF)4Li]{Lu(OSiMe3)[CPMe2)2(SiMe3)]3} (6) obviously by cleavage of silicon grease. A coordination number of eight is observed in the anionic complexes {Ln[C(PMe2) 2(SiMe3)]4Li}, Ln Er (7), Y (8) und La (9). The X-ray crystal structure of 9 verifies the new type of an eightfold phosphorus coordinated lanthanoid center. In compounds Sc[C(PMe2) 2X)]3, X SiMe3 (10a) and X PMe2 (10b) the phosphino-methanide ligands are arranged in an intermediate coordination mode between σ-chelating and π-type coordination as revealed by X-ray diffraction. The X-ray structurally characterized dimeric complex {Sm[CH(PMe2)2]3} 2 (11) combines two different phosphinomethanide coordination modes. Two phosphinomethanide ligands in 11) adopt a π-type coordination, the third ligand is arranged in a η2, μ-C,P fashion.
UR - https://www.scopus.com/pages/publications/0000705972
U2 - 10.1016/0022-328X(94)88197-9
DO - 10.1016/0022-328X(94)88197-9
M3 - Artikel
AN - SCOPUS:0000705972
SN - 0022-328X
VL - 482
SP - 151
EP - 167
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1-2
ER -