N,N′-bis-silylated lithium aryl amidinates: Synthesis, characterization, and the gradual transition of coordination mode from a toward Jt originated by crystal packing interactions

TY - JOUR

T1 - N,N′-bis-silylated lithium aryl amidinates

T2 - Synthesis, characterization, and the gradual transition of coordination mode from a toward Jt originated by crystal packing interactions

AU - Aharonovich, Sinai

AU - Kapon, Moshe

AU - Botoshanski, Mark

AU - Eisen, Moris S.

PY - 2008/4/28

Y1 - 2008/4/28

N2 - In this work nine hthium N,N′-bis(trimethylsilyl)amidinates-TMEDA complexes and the dimeric adduct of 2-ethylbenzonitrile lithium bis(trimethylsilyl)amide were synthesized and characterized. The later compound was found to be a kinetically stabilized intermediate in the amidinate formation. The solid state structures of the amidinates revealed several types of crystalline supramolecular structures, generated by the degree and nature of involvement of the amidinate π system in the intermolecular interactions. The π system was also found to play a significant role in the intramolecular bonding with the lithium atom. The π bonding is obtained at the expense of the o bond, weakening it, while keeping the metal-ligand bond length almost invariable. This facile π interaction along with the Li-N σ-bond activation can imply that similar involvements of the π systems may take place in the salt metathesis reactions with these compounds.

AB - In this work nine hthium N,N′-bis(trimethylsilyl)amidinates-TMEDA complexes and the dimeric adduct of 2-ethylbenzonitrile lithium bis(trimethylsilyl)amide were synthesized and characterized. The later compound was found to be a kinetically stabilized intermediate in the amidinate formation. The solid state structures of the amidinates revealed several types of crystalline supramolecular structures, generated by the degree and nature of involvement of the amidinate π system in the intermolecular interactions. The π system was also found to play a significant role in the intramolecular bonding with the lithium atom. The π bonding is obtained at the expense of the o bond, weakening it, while keeping the metal-ligand bond length almost invariable. This facile π interaction along with the Li-N σ-bond activation can imply that similar involvements of the π systems may take place in the salt metathesis reactions with these compounds.

UR - http://www.scopus.com/inward/record.url?scp=43249109110&partnerID=8YFLogxK

U2 - 10.1021/om701216p

DO - 10.1021/om701216p

M3 - 文章

AN - SCOPUS:43249109110

SN - 0276-7333

VL - 27

SP - 1869

EP - 1877

JO - Organometallics

JF - Organometallics

IS - 8

ER -