TY - JOUR
T1 - Synthesis, structure, dynamic properties, and indenyl transfer reactions of {AlMe2(THF) (indenyl)}2SiMe2
AU - Thiyagarajan, B.
AU - Jordan, Richard F.
AU - Young, Victor G.
PY - 1998/2/2
Y1 - 1998/2/2
N2 - The reaction of Li2SBI (SBI = Me2Si(1-indenyl)2) with 2 equiv of AlMe2Cl in Et2O, followed by treatment with THF, affords {AlMe2(THF)(indenyl)}2-SiMe2 (1), which is isolated as a ca. 1/1 mixture of rac and meso isomers, from which rac-1 is obtained by crystallization from toluene. An X-ray crystallographic analysis establishes that rac-1 exists as the 1,3 isomer, i.e., (1-{AlMe2(THF)-1-indenyl)}(3-{AlMe 2(THF)}-1-indenyl)SiMe2, in the solid state. NMR studies establish that in toluene-d8, rac-1 exists as a 2/1 mixture of 1,3 and 1,1 Al-indenyl isomers which interconvert rapidly on the NMR time scale at room temperature. Rac-1 undergoes slow isomerization to a 1/1 rac/meso mixture (3 days, 23°C, benzene) and also undergoes slow partial disproportionation by ligand redistribution (28% conversion, 2 days, 23°C, benzene). Compound 1 (1/1 to 1.4/1 rac/meso mixture) reacts with Zr(NMe2)4 and Hf(NMe2)4 under mild conditions to yield (SBI)Zr(NMe2)2 in >90% NMR yield (rac/meso = 4.5/1) and rac-(SBI)Hf(NMe2)2 in 61% isolated yield, respectively.
AB - The reaction of Li2SBI (SBI = Me2Si(1-indenyl)2) with 2 equiv of AlMe2Cl in Et2O, followed by treatment with THF, affords {AlMe2(THF)(indenyl)}2-SiMe2 (1), which is isolated as a ca. 1/1 mixture of rac and meso isomers, from which rac-1 is obtained by crystallization from toluene. An X-ray crystallographic analysis establishes that rac-1 exists as the 1,3 isomer, i.e., (1-{AlMe2(THF)-1-indenyl)}(3-{AlMe 2(THF)}-1-indenyl)SiMe2, in the solid state. NMR studies establish that in toluene-d8, rac-1 exists as a 2/1 mixture of 1,3 and 1,1 Al-indenyl isomers which interconvert rapidly on the NMR time scale at room temperature. Rac-1 undergoes slow isomerization to a 1/1 rac/meso mixture (3 days, 23°C, benzene) and also undergoes slow partial disproportionation by ligand redistribution (28% conversion, 2 days, 23°C, benzene). Compound 1 (1/1 to 1.4/1 rac/meso mixture) reacts with Zr(NMe2)4 and Hf(NMe2)4 under mild conditions to yield (SBI)Zr(NMe2)2 in >90% NMR yield (rac/meso = 4.5/1) and rac-(SBI)Hf(NMe2)2 in 61% isolated yield, respectively.
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U2 - 10.1021/om971072a
DO - 10.1021/om971072a
M3 - Article
AN - SCOPUS:0001489334
SN - 0276-7333
VL - 17
SP - 281
EP - 283
JO - Organometallics
JF - Organometallics
IS - 3
ER -