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Title: Tetraaza macrocycles as ancillary ligands in early metal alkyl chemistry. Synthesis and characterization of out-of-plane (Me{sub 4}taen)ZrX{sub 2} (X = alkyl, benzyl, NMe{sub 2}, Cl) and (Me{sub 4}taen)ZrX{sub 2}(NHMe{sub 2}) (X = Cl, CCPh) complexes

Abstract

The objectives of the present work were to develop efficient routes to (Me{sub 4}taen)ZrR{sub 2} compounds and a general understanding of their structures and properties. The chemistry of cationic derivatives will be discussed in a subsequent paper. Alkane elimination reactions of the neutral macrocycle (Me{sub 4}taen)H{sub 2} (1) and homoleptic ZrR{sub 4} compounds provide the most efficient approach to (Me{sub 4}taen)ZrR{sub 2} complexes. Compound 1 reacts readily with ZrR{sub 4} (R = CH{sub 2}Ph, CH{sub 2}SiMe{sub 3}) in pentane at 23{degree}C affording (Me{sub 4}taen)ZrCH{sub 2}Ph{sub 2} (2) and (Me{sub 4}taen)Zr(CH{sub 2}SiMe{sub 3}){sub 2} (3) in high yield. Complexes 2 and 3 are isolated as orange solids after recrystallization and have been characterized by {sup 1}H and {sup 13}C NMR and analysis. Complex 2 is sparingly soluble, 3 is quite soluble in benzene, and both are soluble and stable in THF and CH{sub 2}Cl{sub 2}. The {sup 1}H NMR spectra of 2 and 3 contain singlets for the Me{sub 4}taen methyl and methine hydrogens, and two multiplets for the -CH{sub 2}CH{sub 2}- hydrogens. These data are consistent with cis C{sub 2v}-symmetric structures, in which the `upper` and `lower` -CH{sub 2}CH{sub 2}- hydrogens are inequivalent. The ZrCH{sub 2} J{sub CH} values formore » 2 (106 Hz) and 3 (105 Hz) are at the low end of the normal range observed for alkyl complexes of electropositive metals, and indicate that the hydrocarbyl ligands are not significantly distorted by non-classical {eta}{sup 2}-benzyl or {alpha}-agostic interactions. 50 refs., 6 figs., 11 tabs.« less

Authors:
; ;  [1];  [2]
  1. Univ. of Iowa, Iowa City, IA (United States)
  2. Northern Illinois Univ., DeKalb, IL (United States)
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
81679
DOE Contract Number:  
FG02-88ER13935
Resource Type:
Journal Article
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 14; Journal Issue: 7; Other Information: PBD: Jul 1995
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; ZIRCONIUM COMPOUNDS; SYNTHESIS; CHEMICAL PREPARATION; NMR SPECTRA; ORGANOMETALLIC COMPOUNDS; EXPERIMENTAL DATA; MOLECULAR STRUCTURE; BOND LENGTHS; BOND ANGLE

Citation Formats

Black, D G, Swenson, D C, Jordan, R F, and Rogers, R D. Tetraaza macrocycles as ancillary ligands in early metal alkyl chemistry. Synthesis and characterization of out-of-plane (Me{sub 4}taen)ZrX{sub 2} (X = alkyl, benzyl, NMe{sub 2}, Cl) and (Me{sub 4}taen)ZrX{sub 2}(NHMe{sub 2}) (X = Cl, CCPh) complexes. United States: N. p., 1995. Web. doi:10.1021/om00007a062.
Black, D G, Swenson, D C, Jordan, R F, & Rogers, R D. Tetraaza macrocycles as ancillary ligands in early metal alkyl chemistry. Synthesis and characterization of out-of-plane (Me{sub 4}taen)ZrX{sub 2} (X = alkyl, benzyl, NMe{sub 2}, Cl) and (Me{sub 4}taen)ZrX{sub 2}(NHMe{sub 2}) (X = Cl, CCPh) complexes. United States. doi:10.1021/om00007a062.
Black, D G, Swenson, D C, Jordan, R F, and Rogers, R D. Sat . "Tetraaza macrocycles as ancillary ligands in early metal alkyl chemistry. Synthesis and characterization of out-of-plane (Me{sub 4}taen)ZrX{sub 2} (X = alkyl, benzyl, NMe{sub 2}, Cl) and (Me{sub 4}taen)ZrX{sub 2}(NHMe{sub 2}) (X = Cl, CCPh) complexes". United States. doi:10.1021/om00007a062.
@article{osti_81679,
title = {Tetraaza macrocycles as ancillary ligands in early metal alkyl chemistry. Synthesis and characterization of out-of-plane (Me{sub 4}taen)ZrX{sub 2} (X = alkyl, benzyl, NMe{sub 2}, Cl) and (Me{sub 4}taen)ZrX{sub 2}(NHMe{sub 2}) (X = Cl, CCPh) complexes},
author = {Black, D G and Swenson, D C and Jordan, R F and Rogers, R D},
abstractNote = {The objectives of the present work were to develop efficient routes to (Me{sub 4}taen)ZrR{sub 2} compounds and a general understanding of their structures and properties. The chemistry of cationic derivatives will be discussed in a subsequent paper. Alkane elimination reactions of the neutral macrocycle (Me{sub 4}taen)H{sub 2} (1) and homoleptic ZrR{sub 4} compounds provide the most efficient approach to (Me{sub 4}taen)ZrR{sub 2} complexes. Compound 1 reacts readily with ZrR{sub 4} (R = CH{sub 2}Ph, CH{sub 2}SiMe{sub 3}) in pentane at 23{degree}C affording (Me{sub 4}taen)ZrCH{sub 2}Ph{sub 2} (2) and (Me{sub 4}taen)Zr(CH{sub 2}SiMe{sub 3}){sub 2} (3) in high yield. Complexes 2 and 3 are isolated as orange solids after recrystallization and have been characterized by {sup 1}H and {sup 13}C NMR and analysis. Complex 2 is sparingly soluble, 3 is quite soluble in benzene, and both are soluble and stable in THF and CH{sub 2}Cl{sub 2}. The {sup 1}H NMR spectra of 2 and 3 contain singlets for the Me{sub 4}taen methyl and methine hydrogens, and two multiplets for the -CH{sub 2}CH{sub 2}- hydrogens. These data are consistent with cis C{sub 2v}-symmetric structures, in which the `upper` and `lower` -CH{sub 2}CH{sub 2}- hydrogens are inequivalent. The ZrCH{sub 2} J{sub CH} values for 2 (106 Hz) and 3 (105 Hz) are at the low end of the normal range observed for alkyl complexes of electropositive metals, and indicate that the hydrocarbyl ligands are not significantly distorted by non-classical {eta}{sup 2}-benzyl or {alpha}-agostic interactions. 50 refs., 6 figs., 11 tabs.},
doi = {10.1021/om00007a062},
journal = {Organometallics},
number = 7,
volume = 14,
place = {United States},
year = {1995},
month = {7}
}