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Title: FcTp( R ) ( R = i Pr or t Bu): third-generation ferrocenyl scorpionates

Abstract

Scorpionate (or trispyrazolylborate) ligands have seen much structural variation due to the relative ease of modifying their electronic and steric effects. Second-generation scorpionates were created by increasing the bulk in the 3-position of the pyrazole (pz) ring. A new class of third-generation scorpionates was obtained by modifying the remaining boron substituent. A series of thallium(I) and cobalt(II) complexes of the ferrocenyltris(3-R-pyrazolyl)borate ligand [FcTp R;R= isopropyl ( iPr) ortert-butyl ( tBu)] have been synthesized in order to expand the range of redox-active third-generation scorpionates. These are [ferrocenyltris(3-tert-butylpyrazol-1-yl-κN 2)borato]thallium(I), [FeTl(C 5H 5)(C 26H 37BN 6)], [ferrocenyltris(3-isopropylpyrazol-1-yl-κN 2)borato]thallium(I), [FeTl(C 5H 5)(C 23H 31BN 6)], chlorido[ferrocenyltris(3-tert-butylpyrazol-1-yl-κN 2)borato]cobalt(II), [CoFe(C 5H 5)(C 26H 37BN 6)Cl], [ferrocenyltris(3-tert-butylpyrazol-1-yl-κN 2)borato]iodidocobalt(II) benzene disolvate, [CoFe(C 5H 5)(C 26H 37BN 6)I]·2C 6H 6, and [ferrocenyltris(3-isopropylpyrazol-1-yl-κN 2)borato]iodidocobalt(II), [CoFe(C 5H 5)(C 23H 31BN 6)I]. The structures demonstrate that the metal coordination site can easily be modified by using bulkier substituents at the pz 3-position.

Authors:
ORCiD logo; ORCiD logo; ORCiD logo;
Publication Date:
Research Org.:
Univ. of Delaware, Newark, DE (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1536594
DOE Contract Number:  
FG02-92ER14273
Resource Type:
Journal Article
Journal Name:
Acta Crystallographica. Section C, Structural Chemistry (Online)
Additional Journal Information:
Journal Volume: 72; Journal Issue: 11; Journal ID: ISSN 2053-2296
Publisher:
International Union of Crystallography
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Crystallography

Citation Formats

Sirianni, Eric R., Cummins, Daniel C., Yap, Glenn P. A., and Theopold, Klaus H. FcTp( R ) ( R = i Pr or t Bu): third-generation ferrocenyl scorpionates. United States: N. p., 2016. Web. doi:10.1107/s205322961601202x.
Sirianni, Eric R., Cummins, Daniel C., Yap, Glenn P. A., & Theopold, Klaus H. FcTp( R ) ( R = i Pr or t Bu): third-generation ferrocenyl scorpionates. United States. doi:10.1107/s205322961601202x.
Sirianni, Eric R., Cummins, Daniel C., Yap, Glenn P. A., and Theopold, Klaus H. Wed . "FcTp( R ) ( R = i Pr or t Bu): third-generation ferrocenyl scorpionates". United States. doi:10.1107/s205322961601202x.
@article{osti_1536594,
title = {FcTp( R ) ( R = i Pr or t Bu): third-generation ferrocenyl scorpionates},
author = {Sirianni, Eric R. and Cummins, Daniel C. and Yap, Glenn P. A. and Theopold, Klaus H.},
abstractNote = {Scorpionate (or trispyrazolylborate) ligands have seen much structural variation due to the relative ease of modifying their electronic and steric effects. Second-generation scorpionates were created by increasing the bulk in the 3-position of the pyrazole (pz) ring. A new class of third-generation scorpionates was obtained by modifying the remaining boron substituent. A series of thallium(I) and cobalt(II) complexes of the ferrocenyltris(3-R-pyrazolyl)borate ligand [FcTpR;R= isopropyl (iPr) ortert-butyl (tBu)] have been synthesized in order to expand the range of redox-active third-generation scorpionates. These are [ferrocenyltris(3-tert-butylpyrazol-1-yl-κN2)borato]thallium(I), [FeTl(C5H5)(C26H37BN6)], [ferrocenyltris(3-isopropylpyrazol-1-yl-κN2)borato]thallium(I), [FeTl(C5H5)(C23H31BN6)], chlorido[ferrocenyltris(3-tert-butylpyrazol-1-yl-κN2)borato]cobalt(II), [CoFe(C5H5)(C26H37BN6)Cl], [ferrocenyltris(3-tert-butylpyrazol-1-yl-κN2)borato]iodidocobalt(II) benzene disolvate, [CoFe(C5H5)(C26H37BN6)I]·2C6H6, and [ferrocenyltris(3-isopropylpyrazol-1-yl-κN2)borato]iodidocobalt(II), [CoFe(C5H5)(C23H31BN6)I]. The structures demonstrate that the metal coordination site can easily be modified by using bulkier substituents at the pz 3-position.},
doi = {10.1107/s205322961601202x},
journal = {Acta Crystallographica. Section C, Structural Chemistry (Online)},
issn = {2053-2296},
number = 11,
volume = 72,
place = {United States},
year = {2016},
month = {10}
}