TY - JOUR
T1 - Zirconium complexes of a cyclopentadienylamido ligand with a pendant amine donor via amine and alkane elimination
AU - Mu, Ying
AU - Piers, Warren E.
AU - MacQuarrie, Donald C.
AU - Zaworotko, Michael J.
PY - 1996
Y1 - 1996
N2 - Zirconium complexes of the multidentate ligand CpHNMeSiN(H)R (SiNR = -SiMe2N-t-butyl; NMe = -CH2CH2NMe2, 1) were prepared and characterized via amine and alkane elimination procedures. Reaction of 1 with Zr(NMe2)4 gave a mixture of bis-amido complexes 2 in which the ligand was 1,2 and 1,3 substituted. This mixture was converted to the analogous dichlorides 3 using Me2NH·HCl and 1,3-3 was purified at this stage; alternatively, 1,3-3 was obtained in one pot from 1 and Zr(NMe2)4 in ≈70% yield. Conversion of 1,3-3 to dimethyl compound (CpNMeSiNR)Zr(CH3)2, 1,3-4, was accomplished via reaction of the dichloride with methyllithium; methide abstraction with the Lewis acids B(C6F5)3 and [Ph3C]+[B(C6F5)4] generated the cationic alkyls [(CpNMeSiNR)Zr(CH3)]+[R′B(C 6F5)3]- (R′ = CH3, 6a; C6F5, 6b), which were characterized by NMR spectroscopy. Zirconium complexes containing 1 ligated as its 1,2 isomer were obtained from alkane elimination reactions between 1 and in situ prepared RnZrCl4-n (R = CH3, n = 3; R = CH2SiMe3, n = 2). 1,2-3 and the methyl chloride complex 1,2-(CpNMeSiNR)Zr(CH3)Cl, 5, were obtained in 18 and 30% yield, respectively. Complex 5 was characterized by X-ray crystallography (monoclinic, space group P 21/a, a = 9.6951(10) Å, b = 14.3794(16) Å, c = 14.364(3) Å, V = 1990.3(5) Å3, Z = 4, R = 0.046, Rw = 0.041.).
AB - Zirconium complexes of the multidentate ligand CpHNMeSiN(H)R (SiNR = -SiMe2N-t-butyl; NMe = -CH2CH2NMe2, 1) were prepared and characterized via amine and alkane elimination procedures. Reaction of 1 with Zr(NMe2)4 gave a mixture of bis-amido complexes 2 in which the ligand was 1,2 and 1,3 substituted. This mixture was converted to the analogous dichlorides 3 using Me2NH·HCl and 1,3-3 was purified at this stage; alternatively, 1,3-3 was obtained in one pot from 1 and Zr(NMe2)4 in ≈70% yield. Conversion of 1,3-3 to dimethyl compound (CpNMeSiNR)Zr(CH3)2, 1,3-4, was accomplished via reaction of the dichloride with methyllithium; methide abstraction with the Lewis acids B(C6F5)3 and [Ph3C]+[B(C6F5)4] generated the cationic alkyls [(CpNMeSiNR)Zr(CH3)]+[R′B(C 6F5)3]- (R′ = CH3, 6a; C6F5, 6b), which were characterized by NMR spectroscopy. Zirconium complexes containing 1 ligated as its 1,2 isomer were obtained from alkane elimination reactions between 1 and in situ prepared RnZrCl4-n (R = CH3, n = 3; R = CH2SiMe3, n = 2). 1,2-3 and the methyl chloride complex 1,2-(CpNMeSiNR)Zr(CH3)Cl, 5, were obtained in 18 and 30% yield, respectively. Complex 5 was characterized by X-ray crystallography (monoclinic, space group P 21/a, a = 9.6951(10) Å, b = 14.3794(16) Å, c = 14.364(3) Å, V = 1990.3(5) Å3, Z = 4, R = 0.046, Rw = 0.041.).
KW - Amine elimination
KW - Cp-amido
KW - Zirconium complexes
UR - http://www.scopus.com/inward/record.url?scp=0030230684&partnerID=8YFLogxK
U2 - 10.1139/v96-186
DO - 10.1139/v96-186
M3 - Article
AN - SCOPUS:0030230684
SN - 0008-4042
VL - 74
SP - 1696
EP - 1703
JO - Canadian Journal of Chemistry
JF - Canadian Journal of Chemistry
IS - 9
ER -