Correlated Coordination and Redox Activity of a Hemilabile Noninnocent Ligand in Nickel Complexes

The compound [Ni(QM)2], QM=4,6‐di‐tert‐butyl‐N‐(2‐methylthiomethylphenyl)‐o‐iminobenzoquinone, is a singlet diradical species with approximately planar configuration at the tetracoordinate metal atom and without any NiS bonding interaction. One‐electron oxidation results in additional twofold NiS...

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Veröffentlicht in:Chemistry : a European journal Jg. 20; H. 18; S. 5414 - 5422
Hauptverfasser: Paretzki, Alexa, Bubrin, Martina, Fiedler, Jan, Záliš, Stanislav, Kaim, Wolfgang
Format: Journal Article
Sprache:Englisch
Veröffentlicht: Weinheim WILEY-VCH Verlag 25.04.2014
WILEY‐VCH Verlag
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Schlagworte:
Absorption
Anisotropy
Binding
Cations
Charge transfer
Chemistry
Chemistry, Multidisciplinary
coordination change
Coordination compounds
hemilabile ligands
Ligands
Nickel
noninnocent ligands
Oxidation
Physical Sciences
redox chemistry
Science & Technology
nickel
coordination change
TRANSITION-METAL-COMPLEXES
APPROXIMATION
BEHAVIOR
OXIDATIVE ADDITION
redox chemistry
ELECTRONIC-STRUCTURES
MONONUCLEAR
noninnocent ligands
CHEMISTRY
SYSTEMATICS
ATOMS
hemilabile ligands
4-COORDINATE
ISSN:0947-6539, 1521-3765, 1521-3765
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Abstract The compound [Ni(QM)2], QM=4,6‐di‐tert‐butyl‐N‐(2‐methylthiomethylphenyl)‐o‐iminobenzoquinone, is a singlet diradical species with approximately planar configuration at the tetracoordinate metal atom and without any NiS bonding interaction. One‐electron oxidation results in additional twofold NiS coordination (dNiS≈2.38 Å) to produce a complex cation of [Ni(QM)2](PF6) with hexacoordinate NiII and two distinctly different mer‐configurated tridentate ligands. The O,O′‐trans arrangement in the neutral precursor is changed to an O,O′‐cis configuration in the cation. The EPR signal of [Ni(QM)2](PF6) has a very large g anisotropy and the magnetic measurements indicate an S=3/2 state. The dication was structurally characterized as [Ni(QM)2](ClO4)2 to exhibit a similar NiN2O2S2 framework as the monocation. However, the two tridentate (O,N,S) ligands are now equivalent according to the formulation [NiII(QM0)2]2+. Cyclic voltammetry reflects the qualitative structure change on the first, but not on the second oxidation of [Ni(QM)2], and spectroelectrochemistry reveals a pronounced dependence of the 800–900 nm absorption on the solvent and counterion. Reduction of the neutral form occurs in an electrochemically reversible step to yield an anion with an intense near‐infrared absorption at 1345 nm (ε=10400 M−1 cm−1) and a conventional g factor splitting for a largely metal‐based spin (S=1/2), suggesting a [(QM.−)NiII(QM2−)]− configuration with a tetracoordinate metal atom with antiferromagnetic NiII–(QM.−) interactions and symmetry‐allowed ligand‐to‐ligand intervalence charge transfer (LLIVCT). Calculations are used to understand the NiS binding activity as induced by remote electron transfer at the iminobenzoquinone redox system. Radical change: Oxidation of the singlet diradical species [NiII(QM.−)2], which contains the hemilabile redox‐active ligand QM, results in coordination of the S‐donor functions and spin‐crossover at the nickel atom, although the electron is removed not from the metal but from the noninnocent chelate ligand (see scheme).
AbstractList The compound [Ni(Q M ) 2 ], Q M =4,6‐di‐ tert ‐butyl‐ N ‐(2‐methylthiomethylphenyl)‐ o ‐iminobenzoquinone, is a singlet diradical species with approximately planar configuration at the tetracoordinate metal atom and without any NiS bonding interaction. One‐electron oxidation results in additional twofold NiS coordination ( d NiS ≈2.38 Å) to produce a complex cation of [Ni(Q M ) 2 ](PF 6 ) with hexacoordinate Ni II and two distinctly different mer ‐configurated tridentate ligands. The O,O′‐ trans arrangement in the neutral precursor is changed to an O,O′‐ cis configuration in the cation. The EPR signal of [Ni(Q M ) 2 ](PF 6 ) has a very large g anisotropy and the magnetic measurements indicate an S =3/2 state. The dication was structurally characterized as [Ni(Q M ) 2 ](ClO 4 ) 2 to exhibit a similar NiN 2 O 2 S 2 framework as the monocation. However, the two tridentate (O,N,S) ligands are now equivalent according to the formulation [Ni II (Q M 0 ) 2 ] 2+ . Cyclic voltammetry reflects the qualitative structure change on the first, but not on the second oxidation of [Ni(Q M ) 2 ], and spectroelectrochemistry reveals a pronounced dependence of the 800–900 nm absorption on the solvent and counterion. Reduction of the neutral form occurs in an electrochemically reversible step to yield an anion with an intense near‐infrared absorption at 1345 nm ( ε =10400 M −1 cm −1 ) and a conventional g factor splitting for a largely metal‐based spin ( S =1/2), suggesting a [(Q M . − )Ni II (Q M 2− )] − configuration with a tetracoordinate metal atom with antiferromagnetic Ni II –(Q M . − ) interactions and symmetry‐allowed ligand‐to‐ligand intervalence charge transfer (LLIVCT). Calculations are used to understand the NiS binding activity as induced by remote electron transfer at the iminobenzoquinone redox system.
The compound [Ni(QM)2], QM = 4,6-di-tert-butyl-N-(2-methylthiomethylphenyl)-o-iminobenzoquinone, is a singlet diradical species with approximately planar configuration at the tetracoordinate metal atom and without any Ni-S bonding interaction. One-electron oxidation results in additional twofold Ni-S coordination (dNi-S ≈2.38 Å) to produce a complex cation of [Ni(QM)2](PF6) with hexacoordinate Ni(II) and two distinctly different mer-configurated tridentate ligands. The O,O'-trans arrangement in the neutral precursor is changed to an O,O'-cis configuration in the cation. The EPR signal of [Ni(QM)2](PF6) has a very large g anisotropy and the magnetic measurements indicate an S = 3/2 state. The dication was structurally characterized as [Ni(QM)2](ClO4)2 to exhibit a similar NiN2O2S2 framework as the monocation. However, the two tridentate (O,N,S) ligands are now equivalent according to the formulation [Ni(II)(QM(0))2](2+). Cyclic voltammetry reflects the qualitative structure change on the first, but not on the second oxidation of [Ni(QM)2], and spectroelectrochemistry reveals a pronounced dependence of the 800-900 nm absorption on the solvent and counterion. Reduction of the neutral form occurs in an electrochemically reversible step to yield an anion with an intense near-infrared absorption at 1345 nm (ε = 10,400 M(-1)  cm(-1)) and a conventional g factor splitting for a largely metal-based spin (S = 1/2), suggesting a [(QM(·-))Ni(II)(QM(2-))](-) configuration with a tetracoordinate metal atom with antiferromagnetic Ni(II)-(QM(·-)) interactions and symmetry-allowed ligand-to-ligand intervalence charge transfer (LLIVCT). Calculations are used to understand the Ni-S binding activity as induced by remote electron transfer at the iminobenzoquinone redox system.
The compound [Ni(Q sub(M)) sub(2)], Q sub(M)=4,6-di-tert-butyl-N-(2-methylthiomethylphenyl)-o -iminobenz oquinone, is a singlet diradical species with approximately planar configuration at the tetracoordinate metal atom and without any Ni-S bonding interaction. One-electron oxidation results in additional twofold Ni-S coordination (d sub(Ni-S) approximately 2.38Aa) to produce a complex cation of [Ni(Q sub(M)) sub(2)](PF sub(6)) with hexacoordinate Ni super(II) and two distinctly different mer-configurated tridentate ligands. The O,O'-trans arrangement in the neutral precursor is changed to an O,O'-cis configuration in the cation. The EPR signal of [Ni(Q sub(M)) sub(2)](PF sub(6)) has a very large g anisotropy and the magnetic measurements indicate an S=3/2 state. The dication was structurally characterized as [Ni(Q sub(M)) sub(2)](ClO sub(4)) sub(2) to exhibit a similar NiN sub(2)O sub(2)S sub(2) framework as the monocation. However, the two tridentate (O,N,S) ligands are now equivalent according to the formulation [Ni super(II)(Q sub(M) super(0)) sub(2)] super(2+). Cyclic voltammetry reflects the qualitative structure change on the first, but not on the second oxidation of [Ni(Q sub(M)) sub(2)], and spectroelectrochemistry reveals a pronounced dependence of the 800-900nm absorption on the solvent and counterion. Reduction of the neutral form occurs in an electrochemically reversible step to yield an anion with an intense near-infrared absorption at 1345nm ( epsilon =10400M super(-1)cm super(-1)) and a conventional g factor splitting for a largely metal-based spin (S=1/2), suggesting a [(Q sub(M) super(.) super(-))Ni super(II) (Q sub(M) super(2-))] super(-) configuration with a tetracoordinate metal atom with antiferromagnetic Ni super(II)-(Q sub(M) super(.) super(-)) interactions and symmetry-allowed ligand-to-ligand intervalence charge transfer (LLIVCT). Calculations are used to understand the Ni-S binding activity as induced by remote electron transfer at the iminobenzoquinone redox system. Radical change: Oxidation of the singlet diradical species [Ni super(II)(Q sub(M) super(.) super(-)) sub(2)], which contains the hemilabile redox-active ligand Q sub(M), results in coordination of the S-donor functions and spin-crossover at the nickel atom, although the electron is removed not from the metal but from the noninnocent chelate ligand (see scheme).
The compound [Ni(Q(M))(2)], Q(M)=4,6-di-tert-butyl-N-(2-methylthiomethylphenyl)-o-iminobenzoquinone, is a singlet diradical species with approximately planar configuration at the tetracoordinate metal atom and without any NiS bonding interaction. One-electron oxidation results in additional twofold NiS coordination (d(NiS)approximate to 2.38 angstrom) to produce a complex cation of [Ni(Q(M))(2)](PF6) with hexacoordinate Ni-II and two distinctly different mer-configurated tridentate ligands. The O,O-trans arrangement in the neutral precursor is changed to an O,O-cis configuration in the cation. The EPR signal of [Ni(Q(M))(2)](PF6) has a very large g anisotropy and the magnetic measurements indicate an S=3/2 state. The dication was structurally characterized as [Ni(Q(M))(2)](ClO4)(2) to exhibit a similar NiN2O2S2 framework as the monocation. However, the two tridentate (O,N,S) ligands are now equivalent according to the formulation [Ni-II(Q(M)(0))(2)](2+). Cyclic voltammetry reflects the qualitative structure change on the first, but not on the second oxidation of [Ni(Q(M))(2)], and spectroelectrochemistry reveals a pronounced dependence of the 800-900nm absorption on the solvent and counterion. Reduction of the neutral form occurs in an electrochemically reversible step to yield an anion with an intense near-infrared absorption at 1345nm (epsilon=10400M(-1)cm(-1)) and a conventional g factor splitting for a largely metal-based spin (S=1/2), suggesting a [(Q(M)(.-))Ni-II(Q(M)(2-))](-) configuration with a tetracoordinate metal atom with antiferromagnetic Ni-II-(Q(M)(.-)) interactions and symmetry-allowed ligand-to-ligand intervalence charge transfer (LLIVCT). Calculations are used to understand the NiS binding activity as induced by remote electron transfer at the iminobenzoquinone redox system.
The compound [Ni(QM)2], QM = 4,6-di-tert-butyl-N-(2-methylthiomethylphenyl)-o-iminobenzoquinone, is a singlet diradical species with approximately planar configuration at the tetracoordinate metal atom and without any Ni-S bonding interaction. One-electron oxidation results in additional twofold Ni-S coordination (dNi-S ≈2.38 Å) to produce a complex cation of [Ni(QM)2](PF6) with hexacoordinate Ni(II) and two distinctly different mer-configurated tridentate ligands. The O,O'-trans arrangement in the neutral precursor is changed to an O,O'-cis configuration in the cation. The EPR signal of [Ni(QM)2](PF6) has a very large g anisotropy and the magnetic measurements indicate an S = 3/2 state. The dication was structurally characterized as [Ni(QM)2](ClO4)2 to exhibit a similar NiN2O2S2 framework as the monocation. However, the two tridentate (O,N,S) ligands are now equivalent according to the formulation [Ni(II)(QM(0))2](2+). Cyclic voltammetry reflects the qualitative structure change on the first, but not on the second oxidation of [Ni(QM)2], and spectroelectrochemistry reveals a pronounced dependence of the 800-900 nm absorption on the solvent and counterion. Reduction of the neutral form occurs in an electrochemically reversible step to yield an anion with an intense near-infrared absorption at 1345 nm (ε = 10,400 M(-1)  cm(-1)) and a conventional g factor splitting for a largely metal-based spin (S = 1/2), suggesting a [(QM(·-))Ni(II)(QM(2-))](-) configuration with a tetracoordinate metal atom with antiferromagnetic Ni(II)-(QM(·-)) interactions and symmetry-allowed ligand-to-ligand intervalence charge transfer (LLIVCT). Calculations are used to understand the Ni-S binding activity as induced by remote electron transfer at the iminobenzoquinone redox system.The compound [Ni(QM)2], QM = 4,6-di-tert-butyl-N-(2-methylthiomethylphenyl)-o-iminobenzoquinone, is a singlet diradical species with approximately planar configuration at the tetracoordinate metal atom and without any Ni-S bonding interaction. One-electron oxidation results in additional twofold Ni-S coordination (dNi-S ≈2.38 Å) to produce a complex cation of [Ni(QM)2](PF6) with hexacoordinate Ni(II) and two distinctly different mer-configurated tridentate ligands. The O,O'-trans arrangement in the neutral precursor is changed to an O,O'-cis configuration in the cation. The EPR signal of [Ni(QM)2](PF6) has a very large g anisotropy and the magnetic measurements indicate an S = 3/2 state. The dication was structurally characterized as [Ni(QM)2](ClO4)2 to exhibit a similar NiN2O2S2 framework as the monocation. However, the two tridentate (O,N,S) ligands are now equivalent according to the formulation [Ni(II)(QM(0))2](2+). Cyclic voltammetry reflects the qualitative structure change on the first, but not on the second oxidation of [Ni(QM)2], and spectroelectrochemistry reveals a pronounced dependence of the 800-900 nm absorption on the solvent and counterion. Reduction of the neutral form occurs in an electrochemically reversible step to yield an anion with an intense near-infrared absorption at 1345 nm (ε = 10,400 M(-1)  cm(-1)) and a conventional g factor splitting for a largely metal-based spin (S = 1/2), suggesting a [(QM(·-))Ni(II)(QM(2-))](-) configuration with a tetracoordinate metal atom with antiferromagnetic Ni(II)-(QM(·-)) interactions and symmetry-allowed ligand-to-ligand intervalence charge transfer (LLIVCT). Calculations are used to understand the Ni-S binding activity as induced by remote electron transfer at the iminobenzoquinone redox system.
The compound [Ni(QM)2], QM=4,6-di-tert-butyl-N-(2-methylthiomethylphenyl)-o-iminobenzoquinone, is a singlet diradical species with approximately planar configuration at the tetracoordinate metal atom and without any NiS bonding interaction. One-electron oxidation results in additional twofold NiS coordination (dNiS[asymptotically =]2.38Å) to produce a complex cation of [Ni(QM)2](PF6) with hexacoordinate NiII and two distinctly different mer-configurated tridentate ligands. The O,O'-trans arrangement in the neutral precursor is changed to an O,O'-cis configuration in the cation. The EPR signal of [Ni(QM)2](PF6) has a very large g anisotropy and the magnetic measurements indicate an S=3/2 state. The dication was structurally characterized as [Ni(QM)2](ClO4)2 to exhibit a similar NiN2O2S2 framework as the monocation. However, the two tridentate (O,N,S) ligands are now equivalent according to the formulation [NiII(QM0)2]2+. Cyclic voltammetry reflects the qualitative structure change on the first, but not on the second oxidation of [Ni(QM)2], and spectroelectrochemistry reveals a pronounced dependence of the 800-900nm absorption on the solvent and counterion. Reduction of the neutral form occurs in an electrochemically reversible step to yield an anion with an intense near-infrared absorption at 1345nm ([epsi]=10400M-1cm-1) and a conventional g factor splitting for a largely metal-based spin (S=1/2), suggesting a [(QM.-)NiII(QM2-)]- configuration with a tetracoordinate metal atom with antiferromagnetic NiII-(QM.-) interactions and symmetry-allowed ligand-to-ligand intervalence charge transfer (LLIVCT). Calculations are used to understand the NiS binding activity as induced by remote electron transfer at the iminobenzoquinone redox system. [PUBLICATION ABSTRACT]
The compound [Ni(QM)2], QM=4,6‐di‐tert‐butyl‐N‐(2‐methylthiomethylphenyl)‐o‐iminobenzoquinone, is a singlet diradical species with approximately planar configuration at the tetracoordinate metal atom and without any NiS bonding interaction. One‐electron oxidation results in additional twofold NiS coordination (dNiS≈2.38 Å) to produce a complex cation of [Ni(QM)2](PF6) with hexacoordinate NiII and two distinctly different mer‐configurated tridentate ligands. The O,O′‐trans arrangement in the neutral precursor is changed to an O,O′‐cis configuration in the cation. The EPR signal of [Ni(QM)2](PF6) has a very large g anisotropy and the magnetic measurements indicate an S=3/2 state. The dication was structurally characterized as [Ni(QM)2](ClO4)2 to exhibit a similar NiN2O2S2 framework as the monocation. However, the two tridentate (O,N,S) ligands are now equivalent according to the formulation [NiII(QM0)2]2+. Cyclic voltammetry reflects the qualitative structure change on the first, but not on the second oxidation of [Ni(QM)2], and spectroelectrochemistry reveals a pronounced dependence of the 800–900 nm absorption on the solvent and counterion. Reduction of the neutral form occurs in an electrochemically reversible step to yield an anion with an intense near‐infrared absorption at 1345 nm (ε=10400 M−1 cm−1) and a conventional g factor splitting for a largely metal‐based spin (S=1/2), suggesting a [(QM.−)NiII(QM2−)]− configuration with a tetracoordinate metal atom with antiferromagnetic NiII–(QM.−) interactions and symmetry‐allowed ligand‐to‐ligand intervalence charge transfer (LLIVCT). Calculations are used to understand the NiS binding activity as induced by remote electron transfer at the iminobenzoquinone redox system. Radical change: Oxidation of the singlet diradical species [NiII(QM.−)2], which contains the hemilabile redox‐active ligand QM, results in coordination of the S‐donor functions and spin‐crossover at the nickel atom, although the electron is removed not from the metal but from the noninnocent chelate ligand (see scheme).
Author Záliš, Stanislav
Fiedler, Jan
Paretzki, Alexa
Bubrin, Martina
Kaim, Wolfgang
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  surname: Paretzki
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  givenname: Martina
  surname: Bubrin
  fullname: Bubrin, Martina
  organization: Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70550 Stuttgart (Germany)
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  givenname: Jan
  surname: Fiedler
  fullname: Fiedler, Jan
  organization: J. Heyrovský Institute of Physical Chemistry v.v.i., Academy of Sciences of the Czech Republic, Dolejškova 3, 18223 Prague (Czech Republic)
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  givenname: Stanislav
  surname: Záliš
  fullname: Záliš, Stanislav
  organization: J. Heyrovský Institute of Physical Chemistry v.v.i., Academy of Sciences of the Czech Republic, Dolejškova 3, 18223 Prague (Czech Republic)
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  givenname: Wolfgang
  surname: Kaim
  fullname: Kaim, Wolfgang
  email: kaim@iac.uni-stuttgart.de
  organization: Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70550 Stuttgart (Germany)
BackLink https://www.ncbi.nlm.nih.gov/pubmed/24665084$$D View this record in MEDLINE/PubMed
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Copyright 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Issue 18
Keywords nickel
coordination change
TRANSITION-METAL-COMPLEXES
APPROXIMATION
BEHAVIOR
OXIDATIVE ADDITION
redox chemistry
ELECTRONIC-STRUCTURES
MONONUCLEAR
noninnocent ligands
CHEMISTRY
SYSTEMATICS
ATOMS
hemilabile ligands
4-COORDINATE
Language English
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2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Ministry of Education of the Czech Republic - No. LD11086
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1979; 18
2001; 123
1987; 76
2012
2006; 12
2011
1984; 49
2008; A64
1986; 33
1988; 38
2009; 253
2011; 50A
2011; 30
2007
1996; 96
2002; 655
2003
2001; 22
2005; 44
2009; 48
2012; 51
1991; 317
1996; 77
1965; 87
2002; 41
2006; 45
2010; 29
2001 2001; 113 40
1988; 27
2006; 25
2003; 24
1999; 110
2013; 113
2012 2012; 124 51
1995; 103
2014
1990; 112
2003; 125
1966; 88
2008; 130
2005; 11
2005 2005; 117 44
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Blackmore, KJ (WOS:000231030900006) 2005; 44
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Knödler, A (WOS:000176957500027) 2002; 655
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Connelly, NG (WOS:A1996UC45100009) 1996; 96
Braunstein, P. (000334879500029.16) 2001; 113
Ringenberg, MR (WOS:000252426300005) 2008; 130
Chaudhuri, P (WOS:000167631400013) 2001; 123
Ye, S. (000334879500029.58) 2005; 117
Chirik, PJ (WOS:000295602500001) 2011; 50
Caulton, KG (WOS:000301489600009) 2012
Boyer, JL (WOS:000262430800030) 2009; 48
CHUPP, JP (WOS:A1984TU53200025) 1984; 49
Cossi, M (WOS:000181993100001) 2003; 24
Siri, O (WOS:000234038100012) 2005; 11
Hübner, R (WOS:000288470900024) 2011; 30
PERDEW, JP (WOS:A1986C899500063) 1986; 33
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Chlopek, K (WOS:000239394300032) 2006; 45
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Herebian, D (WOS:000185154300042) 2003; 125
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Machan, C. W. (000334879500029.36) 2012; 124
Ringenberg, MR (WOS:000276692100015) 2010; 29
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References_xml – reference: O. Rotthaus, F. Thomas, O. Jarjayes, C. Philouze, E. Saint-Aman, J.-L. Pierre, Chem. Eur. J. 2006, 12, 6953.
– reference: Angew. Chem. Int. Ed. 2012, 51, 1469 and references cited.
– reference: R. Hübner, S. Weber, S. Strobel, B. Sarkar, S. Záliš, W. Kaim, Organometallics 2011, 30, 1414.
– reference: J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 1996, 77, 3865.
– reference: V. Bachler, G. Olbrich, F. Neese, K. Wieghardt, Inorg. Chem. 2002, 41, 4179.
– reference: D. Herebian, K. E. Wieghardt, F. Neese, J. Am. Chem. Soc. 2003, 125, 10997.
– reference: A. L. Balch, F. Röhrscheid, R. H. Holm, J. Am. Chem. Soc. 1965, 87, 2301;
– reference: G. te Velde, F. M. Bickelhaupt, S. J. A. van Gisbergen, C. Fonseca Guerra, E. J. Baerends, J. G. Snijders, T. Ziegler, J. Comput. Chem. 2001, 22, 931.
– reference: P. Chaudhuri, C. N. Verdani, E. Bill, E. Bothe, T. Weyhermüller, K. Wieghardt, J. Am. Chem. Soc. 2001, 123, 2213.
– reference: M. R. Ringenberg, M. J. Nilges, T. B. Rauchfuss, S. R. Wilson, Organometallics 2010, 29, 1956;
– reference: J. P. Chupp, T. M. Balthazor, M. J. Miller, M. J. Pozzo, J. Org. Chem. 1984, 49, 4711.
– reference: L. A. Curtiss, M. P. McGrath, J.-P. Blaudeau, N. E. Davis, R. C. Binning Jr., L. Radom, J. Chem. Phys. 1995, 103, 6104.
– reference: P. Braunstein, F. Naud, Angew. Chem. 2001, 113, 702;
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– reference: X. Sun, H. Chun, K. Hildenbrand, E. Bothe, T. Weyhermüller, F. Neese, K. Wieghardt, Inorg. Chem. 2002, 41, 4295;
– reference: K. Chlopek, E. Bothe, F. Neese, T. Weyhermüller, K. Wieghardt, Inorg. Chem. 2006, 45, 6298;
– reference: M. Krejčik, M. Danek, F. Hartl, J. Electroanal. Chem. Interfacial Electrochem. 1991, 317, 179;
– reference: M. R. Ringenberg, S. L. Kokatam, Z. M. Heiden, T. B. Rauchfuss, J. Am. Chem. Soc. 2008, 130, 788;
– reference: C. Adamo, V. Barone, J. Chem. Phys. 1999, 110, 6158.
– reference: K. Sik Min, T. Weyhermüller, K. Wieghardt, Dalton Trans. 2003, 1126;
– reference: K. Ray, T. Petrenko, K. Wieghardt, F. Neese, Dalton Trans. 2007, 1552.
– reference: S. Roy, B. Sarkar, D. Bubrin, M. Niemeyer, S. Zališ, G. K. Lahiri, W. Kaim, J. Am. Chem. Soc. 2008, 130, 15230.
– reference: Angew. Chem. Int. Ed. 2005, 44, 2103.
– reference: A. Mukherjee, R. Mukherjee, Indian J. Chem. 2011, 50A, 484.
– reference: A. D. Becke, Phys. Rev. A 1988, 38, 3098.
– reference: S. N. Brown, Inorg. Chem. 2012, 51, 1251.
– reference: A. L. Balch, R. H. Holm, J. Am. Chem. Soc. 1966, 88, 5201.
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Snippet The compound [Ni(QM)2], QM=4,6‐di‐tert‐butyl‐N‐(2‐methylthiomethylphenyl)‐o‐iminobenzoquinone, is a singlet diradical species with approximately planar...
The compound [Ni(Q M ) 2 ], Q M =4,6‐di‐ tert ‐butyl‐ N ‐(2‐methylthiomethylphenyl)‐ o ‐iminobenzoquinone, is a singlet diradical species with approximately...
The compound [Ni(Q(M))(2)], Q(M)=4,6-di-tert-butyl-N-(2-methylthiomethylphenyl)-o-iminobenzoquinone, is a singlet diradical species with approximately planar...
The compound [Ni(QM)2], QM = 4,6-di-tert-butyl-N-(2-methylthiomethylphenyl)-o-iminobenzoquinone, is a singlet diradical species with approximately planar...
The compound [Ni(QM)2], QM=4,6-di-tert-butyl-N-(2-methylthiomethylphenyl)-o-iminobenzoquinone, is a singlet diradical species with approximately planar...
The compound [Ni(Q sub(M)) sub(2)], Q sub(M)=4,6-di-tert-butyl-N-(2-methylthiomethylphenyl)-o -iminobenz oquinone, is a singlet diradical species with...
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SubjectTerms Absorption
Anisotropy
Binding
Cations
Charge transfer
Chemistry
Chemistry, Multidisciplinary
coordination change
Coordination compounds
hemilabile ligands
Ligands
Nickel
noninnocent ligands
Oxidation
Physical Sciences
redox chemistry
Science & Technology
Title Correlated Coordination and Redox Activity of a Hemilabile Noninnocent Ligand in Nickel Complexes
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https://www.proquest.com/docview/1519259976
https://www.proquest.com/docview/1778009452
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