Thermal decomposition of [Me₃SiNCH₂CH₂NSiMe₃] · Li₂(THF)₂ to [LiN(SiMe3)₂ · THF]₂ via a 1,4-trimethylsilyl shift

TY - JOUR

T1 - Thermal decomposition of [Me3SiNCH2CH2NSiMe3] · Li2(THF)2 to [LiN(SiMe3)2 · THF]2 via a 1,4-trimethylsilyl shift

AU - Mack, Helmut

AU - Frenzen, Gerlinde

AU - Bendikov, Michael

AU - Eisen, Moris S.

N1 - Funding Information: This research was supported by the Technion V.P.R. F!jnd Promotion of Sponsored Research. H.M. thanks the Max-Planck-Gesellschaft for a MINERVA postdoctoral fellowship. The authors thank the Minerva Center for Computational Quantum Chemistry, Tech-nion, Haifa, for computational time and Professor Y. Apeloig.

PY - 1997/12/18

Y1 - 1997/12/18

N2 - The dilithium salt [Me3SiNCH2CH2NSiMe3] · Li2(THF)2 decomposes slowly upon heating forming a metastable structure of the crystalline [LiN(SiMe3) · THF]2. The crystal structure of the new form was established by single crystal X-ray diffraction showing a decrease in the a and b parameter values of the unit cell, and an expansion of the c value as compared with the structure obtained at room temperature. The major discrepancies among the known and the metastable crystalline framework are the Li-O bond length and the dihedral angle disposition of the trimethylsilyl groups as regarded to the middle Li-N-Li-N heterocyclobutane ring. Attempts to trap the expected additional lithium imine product were unsuccessful although quenching experiments produced polyethyleneimine.

AB - The dilithium salt [Me3SiNCH2CH2NSiMe3] · Li2(THF)2 decomposes slowly upon heating forming a metastable structure of the crystalline [LiN(SiMe3) · THF]2. The crystal structure of the new form was established by single crystal X-ray diffraction showing a decrease in the a and b parameter values of the unit cell, and an expansion of the c value as compared with the structure obtained at room temperature. The major discrepancies among the known and the metastable crystalline framework are the Li-O bond length and the dihedral angle disposition of the trimethylsilyl groups as regarded to the middle Li-N-Li-N heterocyclobutane ring. Attempts to trap the expected additional lithium imine product were unsuccessful although quenching experiments produced polyethyleneimine.

KW - Lithium amide

KW - Polyethyleneimine

KW - TMS-shift

KW - X-ray crystal structure

UR - http://www.scopus.com/inward/record.url?scp=0031577813&partnerID=8YFLogxK

U2 - 10.1016/S0022-328X(97)00270-2

DO - 10.1016/S0022-328X(97)00270-2

M3 - 文章

AN - SCOPUS:0031577813

SN - 0022-328X

VL - 549

SP - 39

EP - 43

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -