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Polypyrazolylborates: Scorpionates
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Abstract
Polypyrazolylborates, also known as scorpionates because of certain specific features of their coordination chemistry, are a large class of user-friendly ligands, capable of being fine-tuned through appropriate substitution on the pyrazolyl rings. They have had significant impact on many areas of coordination and organometallic chemistry. They were particularly useful in modeling a number of enzymes, involving numerous metals, not just in matching or approaching their spectroscopic features, but also exhibiting some of their catalytic activity. Key features of the ligands and examples of their use in modeling biologically active compounds are briefly presented. Recently, a number of analogous scorpionate ligands has been developed, which contain a tetrasubstituted borate anion, with soft donor functionalities on the substituents, such as thioethers or disubstituted phosphines. Some of them form six-membered rings when coordinated to a metal ion, and others form flexible eight-membered rings.
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Second-Year UndergraduateKeywords (Domain):
Inorganic ChemistryKeywords (Feature):
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Coordination CompoundsCiting Articles
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This article has been cited by 5 ACS Journal articles (5 most recent appear below).
Structures, Physicochemical Properties, and Reactivities of Cobalt(II) Complexes Supported by a Homoscorpionate (Tris(pyrazolyl)borate) Ligand TpPh,Me
Atsushi Kunishita, Thomas L. Gianetti, and John ArnoldOrganometallics2012 31 (1), 372-380Structures, Physicochemical Properties, and Reactivities of Cobalt(II) Complexes Supported by a Homoscorpionate (Tris(pyrazolyl)borate) Ligand TpPh,Me
Atsushi Kunishita, Thomas L. Gianetti, and John ArnoldOrganometallics2012 31 (1), 372-380The coordination chemistry of a mononuclear cobalt complex supported by the monoanionic hydrotris(pyrazolyl)borate tridentate ligand [TpPh,Me] containing substituted phenyl groups at the 3-position of the pyrazole rings and methyl groups at the 5-position ...
Phospha-Scorpionate Complexes by Click Chemistry using Phenyl Azide and Ethynylphosphine Oxides
Sander G. A. van Assema, Cornelis G. J. Tazelaar, G. Bas de Jong, Jan H. van Maarseveen, Marius Schakel, Martin Lutz, Anthony L. Spek, J. Chris Slootweg and Koop LammertsmaOrganometallics2008 27 (13), 3210-3215Phospha-Scorpionate Complexes by Click Chemistry using Phenyl Azide and Ethynylphosphine Oxides
Sander G. A. van Assema, Cornelis G. J. Tazelaar, G. Bas de Jong, Jan H. van Maarseveen, Marius Schakel, Martin Lutz, Anthony L. Spek, J. Chris Slootweg and Koop LammertsmaOrganometallics2008 27 (13), 3210-3215The copper-catalyzed Click reaction of phenyl azide with ethynylphosphine oxides provides new P-substituted triazoles. With tris(ethynyl)phosphine oxide this route affords a versatile scorpionate ligand that coordinates to RhCl3 as a tripodal N ligand. ...
Density Functional Theory Study of the Binding Capability of Tris(pyrazol-1-yl)methane toward Cu(I) and Ag(I) Cations
Maurizio Casarin, Daniel Forrer, Federica Garau, Luciano Pandolfo, Claudio Pettinari and Andrea VittadiniThe Journal of Physical Chemistry A2008 112 (29), 6723-6731Density Functional Theory Study of the Binding Capability of Tris(pyrazol-1-yl)methane toward Cu(I) and Ag(I) Cations
Maurizio Casarin, Daniel Forrer, Federica Garau, Luciano Pandolfo, Claudio Pettinari and Andrea VittadiniThe Journal of Physical Chemistry A2008 112 (29), 6723-6731Density functional theory (DFT) has been used to look into the electronic structure of [M(tpm)]+ molecular ion conformers (M = Cu, Ag; tpm = tris(pyrazol-1-yl)methane) and to study the energetics of their interconversion. Theoretical data pertaining to ...
Preparation, Spectroscopic Characterization, X-ray Structure, and Theoretical Investigation of Hydride−, Dihydrogen−, and Acetone−OsTp Complexes: A Hydridotris(pyrazolyl)borate−Cyclopentadienyl Comparison
Ruth Castro-Rodrigo, Miguel A. Esteruelas, Ana M. López, Montserrat Oliván, and Enrique OñateOrganometallics2007 26 (18), 4498-4509Preparation, Spectroscopic Characterization, X-ray Structure, and Theoretical Investigation of Hydride−, Dihydrogen−, and Acetone−OsTp Complexes: A Hydridotris(pyrazolyl)borate−Cyclopentadienyl Comparison
Ruth Castro-Rodrigo, Miguel A. Esteruelas, Ana M. López, Montserrat Oliván, and Enrique OñateOrganometallics2007 26 (18), 4498-4509A new entry to the OsTp chemistry has been achieved starting from OsH3Cl(PiPr3)2 and KTp. The preparation and characterization of the hydride complexes OsH3(2-Tp)(PiPr3)2, OsH3Tp(PiPr3), and the bis(dihydrogen) derivative [OsTp(2-H2)2(PiPr3)]BF4 are ...
Novel tert-Butyl-tris(3-hydrocarbylpyrazol-1-yl)borate Ligands: Synthesis, Spectroscopic Studies, and Coordination Chemistry
Olivier Graziani, Paul Hamon, Jean-Yves Thépot, Loïc Toupet, Petra Á. Szilágyi, Gábor Molnár, Azzedine Bousseksou, Mats Tilset, and Jean-René HamonInorganic Chemistry2006 45 (14), 5661-5674Novel tert-Butyl-tris(3-hydrocarbylpyrazol-1-yl)borate Ligands: Synthesis, Spectroscopic Studies, and Coordination Chemistry
Olivier Graziani, Paul Hamon, Jean-Yves Thépot, Loïc Toupet, Petra Á. Szilágyi, Gábor Molnár, Azzedine Bousseksou, Mats Tilset, and Jean-René HamonInorganic Chemistry2006 45 (14), 5661-5674A series of five new tert-butyl[tris(3-hydrocarbylpyrazol-1-yl)borate ligands [t-BuTpR]- (R = H, Me, i-Pr, t-Bu, Ph) were synthesized and characterized as their lithium and thallium salts. The partial hydrolysis of Li[t-BuTpt-Bu] afforded the structurally ...
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- Received: August 03, 2009
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