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Title: Synthesis, structure, and reactivity of dimeric mono(cyclopentadienyl)yttrium bis(tert-butoxide) complexes. [(C[sub 5][sub 5])Y([mu]-OCMe[sub 3])(OCMe[sub 3])][sub 2] (C[sub 5]R[sub 5] = C[sub 5]Me[sub 5], C[sub 5]H[sub 5], C[sub 5]H[sub 4]Me, C[sub 5]H[sub 4]SiMe[sub 3], and C[sub 9]H[sub 7])

Abstract

The reaction of Y[sub 3](OR)[sub 7]Cl[sub 2](THF)[sub 2] (R = CMe[sub 3]) with alkali metal cyclopentadienyl reagents, MC[sub 5]R[sub 5] (M = Na or K), in toluene disrupts the trimetallic structure of the starting material and forms the halide-free bimetallic compounds [(C[sub 5]R[sub 5])Y([mu]-OR) (OR)][sub 2] (C[sub 5]R[sub 5] = C[sub 5]Me[sub 5], 1; C[sub 5]H[sub 5], 2; C[sub 5]H[sub 4]Me, 3; C[sub 5]H[sub 4]SiMe[sub 3], 4). 1 and 4 were also obtained from the reaction of YCl[sub 3](THF)[sub x] with 2 equiv of NaOCMe[sub 3] and 1 equiv of MC[sub 5]R[sub 5] in toluene at reflux. Also prepared in this manner was the indenyl analog, [(C[sub 9]H[sub 7])Y([mu]-OR)(OR)][sub 2], 5. X-ray crystallographic data on 1, 2, 4, and 5 reveal that structurally analogous complexes are formed in these reactions despite the different substituents on the cyclopentadienyl rings. In each of these four complexes, the two cyclopentadienyl ligands are arranged in a cis orientation around a (RO)Y([mu]-OR)[sub 2]Y(OR) central core which has similar metrical parameters in each compound. The ligand redistribution product (C[sub 5]H[sub 5])[sub 2]Y([mu]-OR)[sub 2]Y(C[sub 5]H[sub 5])(OR), 6, is also isolated as a minor component in the reaction between Y[sub 3](OR)[sub 7]Cl[sub 2](THF)[sub 2] and NaC[sub 5]H[sub 5].more » 2-5 react with LiCH[sub 2]SiMe[sub 3] to unexpectedly lose LiC[sub 5]R[sub 5] instead of LiOR. 65 refs., 9 figs., 3 tabs.« less

Authors:
; ;  [1]
  1. (Univ. of California, Irvine, CA (United States))
Publication Date:
OSTI Identifier:
5425052
Resource Type:
Journal Article
Journal Name:
Organometallics; (United States)
Additional Journal Information:
Journal Volume: 12:10; Journal ID: ISSN 0276-7333
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMPLEXES; CHEMICAL REACTIONS; CRYSTAL STRUCTURE; MOLECULAR STRUCTURE; SYNTHESIS; DIMERS; LIGANDS; ORGANOMETALLIC COMPOUNDS; YTTRIUM COMPLEXES; ORGANIC COMPOUNDS; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties; 400102 - Chemical & Spectral Procedures

Citation Formats

Evans, W.J., Boyle, T.J., and Ziller, J.W. Synthesis, structure, and reactivity of dimeric mono(cyclopentadienyl)yttrium bis(tert-butoxide) complexes. [(C[sub 5][sub 5])Y([mu]-OCMe[sub 3])(OCMe[sub 3])][sub 2] (C[sub 5]R[sub 5] = C[sub 5]Me[sub 5], C[sub 5]H[sub 5], C[sub 5]H[sub 4]Me, C[sub 5]H[sub 4]SiMe[sub 3], and C[sub 9]H[sub 7]). United States: N. p., 1993. Web. doi:10.1021/om00034a036.
Evans, W.J., Boyle, T.J., & Ziller, J.W. Synthesis, structure, and reactivity of dimeric mono(cyclopentadienyl)yttrium bis(tert-butoxide) complexes. [(C[sub 5][sub 5])Y([mu]-OCMe[sub 3])(OCMe[sub 3])][sub 2] (C[sub 5]R[sub 5] = C[sub 5]Me[sub 5], C[sub 5]H[sub 5], C[sub 5]H[sub 4]Me, C[sub 5]H[sub 4]SiMe[sub 3], and C[sub 9]H[sub 7]). United States. doi:10.1021/om00034a036.
Evans, W.J., Boyle, T.J., and Ziller, J.W. Fri . "Synthesis, structure, and reactivity of dimeric mono(cyclopentadienyl)yttrium bis(tert-butoxide) complexes. [(C[sub 5][sub 5])Y([mu]-OCMe[sub 3])(OCMe[sub 3])][sub 2] (C[sub 5]R[sub 5] = C[sub 5]Me[sub 5], C[sub 5]H[sub 5], C[sub 5]H[sub 4]Me, C[sub 5]H[sub 4]SiMe[sub 3], and C[sub 9]H[sub 7])". United States. doi:10.1021/om00034a036.
@article{osti_5425052,
title = {Synthesis, structure, and reactivity of dimeric mono(cyclopentadienyl)yttrium bis(tert-butoxide) complexes. [(C[sub 5][sub 5])Y([mu]-OCMe[sub 3])(OCMe[sub 3])][sub 2] (C[sub 5]R[sub 5] = C[sub 5]Me[sub 5], C[sub 5]H[sub 5], C[sub 5]H[sub 4]Me, C[sub 5]H[sub 4]SiMe[sub 3], and C[sub 9]H[sub 7])},
author = {Evans, W.J. and Boyle, T.J. and Ziller, J.W.},
abstractNote = {The reaction of Y[sub 3](OR)[sub 7]Cl[sub 2](THF)[sub 2] (R = CMe[sub 3]) with alkali metal cyclopentadienyl reagents, MC[sub 5]R[sub 5] (M = Na or K), in toluene disrupts the trimetallic structure of the starting material and forms the halide-free bimetallic compounds [(C[sub 5]R[sub 5])Y([mu]-OR) (OR)][sub 2] (C[sub 5]R[sub 5] = C[sub 5]Me[sub 5], 1; C[sub 5]H[sub 5], 2; C[sub 5]H[sub 4]Me, 3; C[sub 5]H[sub 4]SiMe[sub 3], 4). 1 and 4 were also obtained from the reaction of YCl[sub 3](THF)[sub x] with 2 equiv of NaOCMe[sub 3] and 1 equiv of MC[sub 5]R[sub 5] in toluene at reflux. Also prepared in this manner was the indenyl analog, [(C[sub 9]H[sub 7])Y([mu]-OR)(OR)][sub 2], 5. X-ray crystallographic data on 1, 2, 4, and 5 reveal that structurally analogous complexes are formed in these reactions despite the different substituents on the cyclopentadienyl rings. In each of these four complexes, the two cyclopentadienyl ligands are arranged in a cis orientation around a (RO)Y([mu]-OR)[sub 2]Y(OR) central core which has similar metrical parameters in each compound. The ligand redistribution product (C[sub 5]H[sub 5])[sub 2]Y([mu]-OR)[sub 2]Y(C[sub 5]H[sub 5])(OR), 6, is also isolated as a minor component in the reaction between Y[sub 3](OR)[sub 7]Cl[sub 2](THF)[sub 2] and NaC[sub 5]H[sub 5]. 2-5 react with LiCH[sub 2]SiMe[sub 3] to unexpectedly lose LiC[sub 5]R[sub 5] instead of LiOR. 65 refs., 9 figs., 3 tabs.},
doi = {10.1021/om00034a036},
journal = {Organometallics; (United States)},
issn = {0276-7333},
number = ,
volume = 12:10,
place = {United States},
year = {1993},
month = {10}
}