Lithium furyl and pyridyl amidinates as building blocks in coordination polymers, ladder and cage structures

TY - JOUR

T1 - Lithium furyl and pyridyl amidinates as building blocks in coordination polymers, ladder and cage structures

AU - Aharonovich, Sinai

AU - Botoshanski, Mark

AU - Rabinovich, Ziv

AU - Waymouth, Robert M.

AU - Eisen, Moris S.

N1 - Funding Information: This work was supported by CICYT grant TAP95-0386 and by Xunta de Galicia, Secretaria Xeral de Investigacion e Desenvolvemento, XUGA 20605B98.

PY - 2010/2/1

Y1 - 2010/2/1

N2 - Lithium N,N′-bis(trimethylsilyl)heterocyclic amidinate complexes with 3- and 4-pyridyl and 3-furyl carbon substituents were prepared by addition of the corresponding nitriles to LiN(SiMe3)2 (LiNTMS 2) solution. In the presence of N,N,N′, N′ tetramethylethylene diamine (TMEDA), both pyridyl amidinates crystallize as coordination polymers with an amidinate-Li-pyridyl backbone. The 4-pyridyl derivative (7) creates a linear polymer with amidinate-Li-TMEDA units as side chains, whereas the 3-pyridyl polymer (6) has a two-dimensional (2D) network structure in which TMEDA serves as a cross-linker. Solvation of the reaction mixture of 3-furonitrile and LiNTMS2 with TMEDA affords the monomeric 3-furyl amidinate Li TMEDA complex (3). Crystals of the Li2O complex {[3-furyl-C-(NTMS)2Li]4 · Li2O) · C7H8 (4) are obtained from toluene by partial hydrolysis of the unsolvated 3-furyl amidinate (2). Degradation of the polymer (7) to monomeric units can be achieved by solvation in toluene or by reaction with TMS2NLi · TMEDA that affords crystals of the complex (NTMS2Li · [4-C5H4N-C(NTMS) 2Li · TMEDA]}2 · (NTMS2Li · TMEDA) (8). The formation of these aggregates can be rationalized by directed substitution of TMEDA with pyridyl moieties and by the laddering principle.

AB - Lithium N,N′-bis(trimethylsilyl)heterocyclic amidinate complexes with 3- and 4-pyridyl and 3-furyl carbon substituents were prepared by addition of the corresponding nitriles to LiN(SiMe3)2 (LiNTMS 2) solution. In the presence of N,N,N′, N′ tetramethylethylene diamine (TMEDA), both pyridyl amidinates crystallize as coordination polymers with an amidinate-Li-pyridyl backbone. The 4-pyridyl derivative (7) creates a linear polymer with amidinate-Li-TMEDA units as side chains, whereas the 3-pyridyl polymer (6) has a two-dimensional (2D) network structure in which TMEDA serves as a cross-linker. Solvation of the reaction mixture of 3-furonitrile and LiNTMS2 with TMEDA affords the monomeric 3-furyl amidinate Li TMEDA complex (3). Crystals of the Li2O complex {[3-furyl-C-(NTMS)2Li]4 · Li2O) · C7H8 (4) are obtained from toluene by partial hydrolysis of the unsolvated 3-furyl amidinate (2). Degradation of the polymer (7) to monomeric units can be achieved by solvation in toluene or by reaction with TMS2NLi · TMEDA that affords crystals of the complex (NTMS2Li · [4-C5H4N-C(NTMS) 2Li · TMEDA]}2 · (NTMS2Li · TMEDA) (8). The formation of these aggregates can be rationalized by directed substitution of TMEDA with pyridyl moieties and by the laddering principle.

UR - http://www.scopus.com/inward/record.url?scp=75649120353&partnerID=8YFLogxK

U2 - 10.1021/ic902183c

DO - 10.1021/ic902183c

M3 - 文章

C2 - 20039691

AN - SCOPUS:75649120353

SN - 0020-1669

VL - 49

SP - 1220

EP - 1229

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 3

ER -