Abstract
The reaction of 2-lithiopyridine and the appropriate diarylketone followed by hydrolysis yields pyCAr2OH pyridine-alcohols (1a, Ar = 4-tBu-C6H4; 1b, pyCAr2OH = 2-pyridyl-9-fluorenol; 1c, Ar = 3-CF3-C6H4; 1d, Ar = 4-Ph-C6H4; 1e, Ar = 4-NEt2-C6H4; 1f, pyCAr2-OH = 1-(2-pyridyl)-1-dibenzosuberol; 1g, Ar = 3,5-(CF3)2-C6H3). The reaction of Ti(NMe2)4 with 2 equiv of 1a-g yields (pyCAr2O)2Ti(NMe2)2 (2a-g) and NMe2H. The reaction of Zr-(NMe2)4 with 2 equiv of 1a,b,e yields (pyCAr2O)2Zr(NMe2)2 (3a,b,e), while similar reactions with 1c,d yield mixtures of (pyCAr2O)xZr(NMe2)4-x (x = 1-3) species. {pyC(3-CF3-C6H4)2O} 3-Zr(NMe2) (4c) and {pyC(4-NEt2-C6H4)2O}4Zr (5e) are prepared from Zr(NMe2)4 and 3 equiv of 1c or 4 equiv of 1e, respectively. The reaction of Hf(NMe2)4 with 2 equiv of 1a,e yields (pyCAr2O)2Hf(NMe2)2 (6a,e), while reaction with 3 equiv of 1b,c yields (pyCAr2O)3Hf(NMe2) (7b,c). X-ray crystallographic analyses establish that 2b, 2e, and 3a adopt distorted octahedral structures with a trans-O, cis-py, cis-amide arrangement of ligands. NMR data show that (pyCAr2O)2M(NMe2)2 complexes adopt the same structure in solution but undergo inversion of configuration at the metal with racemization barriers (ΔG‡ (racemization)) in the range of 12-14 kcal/mol. Treatment of (pyCAr2O)2M(NMe2)2 complexes with Al(iBu)3 and methylalumoxane (MAO) yields active, multisite ethylene polymerization catalysts.
| Original language | English |
|---|---|
| Pages (from-to) | 3314-3323 |
| Number of pages | 10 |
| Journal | Organometallics |
| Volume | 16 |
| Issue number | 15 |
| Publication status | Published - Jul 22 1997 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
Cite this
Synthesis, structures, dynamics, and olefin polymerization behavior of group 4 metal (pyCAr2O)2M(NR2)2 complexes containing bidentate pyridine-alkoxide ancillary ligands. / Kim, Il; Nishihara, Yasushi; Jordan, Richard F.; Rogers, Robin D.; Rheingold, Arnold L.; Yap, Glenn P A.
In: Organometallics, Vol. 16, No. 15, 22.07.1997, p. 3314-3323.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Synthesis, structures, dynamics, and olefin polymerization behavior of group 4 metal (pyCAr2O)2M(NR2)2 complexes containing bidentate pyridine-alkoxide ancillary ligands
AU - Kim, Il
AU - Nishihara, Yasushi
AU - Jordan, Richard F.
AU - Rogers, Robin D.
AU - Rheingold, Arnold L.
AU - Yap, Glenn P A
PY - 1997/7/22
Y1 - 1997/7/22
N2 - The reaction of 2-lithiopyridine and the appropriate diarylketone followed by hydrolysis yields pyCAr2OH pyridine-alcohols (1a, Ar = 4-tBu-C6H4; 1b, pyCAr2OH = 2-pyridyl-9-fluorenol; 1c, Ar = 3-CF3-C6H4; 1d, Ar = 4-Ph-C6H4; 1e, Ar = 4-NEt2-C6H4; 1f, pyCAr2-OH = 1-(2-pyridyl)-1-dibenzosuberol; 1g, Ar = 3,5-(CF3)2-C6H3). The reaction of Ti(NMe2)4 with 2 equiv of 1a-g yields (pyCAr2O)2Ti(NMe2)2 (2a-g) and NMe2H. The reaction of Zr-(NMe2)4 with 2 equiv of 1a,b,e yields (pyCAr2O)2Zr(NMe2)2 (3a,b,e), while similar reactions with 1c,d yield mixtures of (pyCAr2O)xZr(NMe2)4-x (x = 1-3) species. {pyC(3-CF3-C6H4)2O} 3-Zr(NMe2) (4c) and {pyC(4-NEt2-C6H4)2O}4Zr (5e) are prepared from Zr(NMe2)4 and 3 equiv of 1c or 4 equiv of 1e, respectively. The reaction of Hf(NMe2)4 with 2 equiv of 1a,e yields (pyCAr2O)2Hf(NMe2)2 (6a,e), while reaction with 3 equiv of 1b,c yields (pyCAr2O)3Hf(NMe2) (7b,c). X-ray crystallographic analyses establish that 2b, 2e, and 3a adopt distorted octahedral structures with a trans-O, cis-py, cis-amide arrangement of ligands. NMR data show that (pyCAr2O)2M(NMe2)2 complexes adopt the same structure in solution but undergo inversion of configuration at the metal with racemization barriers (ΔG‡ (racemization)) in the range of 12-14 kcal/mol. Treatment of (pyCAr2O)2M(NMe2)2 complexes with Al(iBu)3 and methylalumoxane (MAO) yields active, multisite ethylene polymerization catalysts.
AB - The reaction of 2-lithiopyridine and the appropriate diarylketone followed by hydrolysis yields pyCAr2OH pyridine-alcohols (1a, Ar = 4-tBu-C6H4; 1b, pyCAr2OH = 2-pyridyl-9-fluorenol; 1c, Ar = 3-CF3-C6H4; 1d, Ar = 4-Ph-C6H4; 1e, Ar = 4-NEt2-C6H4; 1f, pyCAr2-OH = 1-(2-pyridyl)-1-dibenzosuberol; 1g, Ar = 3,5-(CF3)2-C6H3). The reaction of Ti(NMe2)4 with 2 equiv of 1a-g yields (pyCAr2O)2Ti(NMe2)2 (2a-g) and NMe2H. The reaction of Zr-(NMe2)4 with 2 equiv of 1a,b,e yields (pyCAr2O)2Zr(NMe2)2 (3a,b,e), while similar reactions with 1c,d yield mixtures of (pyCAr2O)xZr(NMe2)4-x (x = 1-3) species. {pyC(3-CF3-C6H4)2O} 3-Zr(NMe2) (4c) and {pyC(4-NEt2-C6H4)2O}4Zr (5e) are prepared from Zr(NMe2)4 and 3 equiv of 1c or 4 equiv of 1e, respectively. The reaction of Hf(NMe2)4 with 2 equiv of 1a,e yields (pyCAr2O)2Hf(NMe2)2 (6a,e), while reaction with 3 equiv of 1b,c yields (pyCAr2O)3Hf(NMe2) (7b,c). X-ray crystallographic analyses establish that 2b, 2e, and 3a adopt distorted octahedral structures with a trans-O, cis-py, cis-amide arrangement of ligands. NMR data show that (pyCAr2O)2M(NMe2)2 complexes adopt the same structure in solution but undergo inversion of configuration at the metal with racemization barriers (ΔG‡ (racemization)) in the range of 12-14 kcal/mol. Treatment of (pyCAr2O)2M(NMe2)2 complexes with Al(iBu)3 and methylalumoxane (MAO) yields active, multisite ethylene polymerization catalysts.
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UR - http://www.scopus.com/inward/citedby.url?scp=0037642316&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0037642316
VL - 16
SP - 3314
EP - 3323
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 15
ER -