Aromatic Versus Heteroradialene Character in Extended Thiophloroglucinol Ligands and their Trinuclear Nickel(II) Complexes

Feldscher B, Stammler A, Bögge H, Glaser T (2014)
Chemistry - An Asian Journal 9(8): 2205-2218.

Download
Es wurde kein Volltext hochgeladen. Nur Publikationsnachweis!
Zeitschriftenaufsatz | Veröffentlicht | Englisch
Abstract / Bemerkung
Extended phloroglucinol ligands and complexes are best described as nonaromatic heteroradialenes. Herein, the electronic structures of extended thiophloroglucinol ligands and their Ni-3(II) complexes are evaluated by comparison to their phloroglucinol analogs by means of NMR, FTIR, UV/Vis, and structural parameters. To provide a full set of compounds for this comparison of S versus O substitution, a new triplesalen ligand, its Ni-3(II) complex, and a new thiophloroglucinol were synthesized. H-1 and N-15 NMR chemical shifts and coupling constants prove that the thiophloroglucinol ligands exist as the N-protonated and not the O-protonated tautomer. C-13 and N-15 NMR chemical shifts and structural parameters further demonstrated that the extended thiophloroglucinol ligands must be described with a predominant thione-enamine (heteroradialene) character despite the participation of a C=S double bond. In the Ni-3(II) complexes, this heteroradialene character is reduced but still predominant.
Erscheinungsjahr
Zeitschriftentitel
Chemistry - An Asian Journal
Band
9
Ausgabe
8
Seite(n)
2205-2218
ISSN
PUB-ID

Zitieren

Feldscher B, Stammler A, Bögge H, Glaser T. Aromatic Versus Heteroradialene Character in Extended Thiophloroglucinol Ligands and their Trinuclear Nickel(II) Complexes. Chemistry - An Asian Journal. 2014;9(8):2205-2218.
Feldscher, B., Stammler, A., Bögge, H., & Glaser, T. (2014). Aromatic Versus Heteroradialene Character in Extended Thiophloroglucinol Ligands and their Trinuclear Nickel(II) Complexes. Chemistry - An Asian Journal, 9(8), 2205-2218. doi:10.1002/asia.201402272
Feldscher, B., Stammler, A., Bögge, H., and Glaser, T. (2014). Aromatic Versus Heteroradialene Character in Extended Thiophloroglucinol Ligands and their Trinuclear Nickel(II) Complexes. Chemistry - An Asian Journal 9, 2205-2218.
Feldscher, B., et al., 2014. Aromatic Versus Heteroradialene Character in Extended Thiophloroglucinol Ligands and their Trinuclear Nickel(II) Complexes. Chemistry - An Asian Journal, 9(8), p 2205-2218.
B. Feldscher, et al., “Aromatic Versus Heteroradialene Character in Extended Thiophloroglucinol Ligands and their Trinuclear Nickel(II) Complexes”, Chemistry - An Asian Journal, vol. 9, 2014, pp. 2205-2218.
Feldscher, B., Stammler, A., Bögge, H., Glaser, T.: Aromatic Versus Heteroradialene Character in Extended Thiophloroglucinol Ligands and their Trinuclear Nickel(II) Complexes. Chemistry - An Asian Journal. 9, 2205-2218 (2014).
Feldscher, Bastian, Stammler, Anja, Bögge, Hartmut, and Glaser, Thorsten. “Aromatic Versus Heteroradialene Character in Extended Thiophloroglucinol Ligands and their Trinuclear Nickel(II) Complexes”. Chemistry - An Asian Journal 9.8 (2014): 2205-2218.

150 References

Daten bereitgestellt von Europe PubMed Central.


Sessoli, Nature 365(), 1993

Thomas, Nature 383(), 1996

Christou, MRS Bull. 25(), 2000

Gatteschi, 2006

Wernsdorfer, 2007
Supramolecular spin valves.
Urdampilleta M, Klyatskaya S, Cleuziou JP, Ruben M, Wernsdorfer W., Nat Mater 10(7), 2011
PMID: 21685902
Electronic read-out of a single nuclear spin using a molecular spin transistor.
Vincent R, Klyatskaya S, Ruben M, Wernsdorfer W, Balestro F., Nature 488(7411), 2012
PMID: 22895342
Quantum computing in molecular magnets.
Leuenberger MN, Loss D., Nature 410(6830), 2001
PMID: 11298441
Chemical engineering of molecular qubits.
Wedge CJ, Timco GA, Spielberg ET, George RE, Tuna F, Rigby S, McInnes EJ, Winpenny RE, Blundell SJ, Ardavan A., Phys. Rev. Lett. 108(10), 2012
PMID: 22463450
Engineering the coupling between molecular spin qubits by coordination chemistry.
Timco GA, Carretta S, Troiani F, Tuna F, Pritchard RJ, Muryn CA, McInnes EJ, Ghirri A, Candini A, Santini P, Amoretti G, Affronte M, Winpenny RE., Nat Nanotechnol 4(3), 2009
PMID: 19265847
Molecular spintronics using single-molecule magnets.
Bogani L, Wernsdorfer W., Nat Mater 7(3), 2008
PMID: 18297126

Glaser, Dalton Trans. (), 2003
Trinuclear nickel complexes with triplesalen ligands: simultaneous occurrence of mixed valence and valence tautomerism in the oxidized species.
Glaser T, Heidemeier M, Frohlich R, Hildebrandt P, Bothe E, Bill E., Inorg Chem 44(15), 2005
PMID: 16022545
Rational design of single-molecule magnets: a supramolecular approach.
Glaser T., Chem. Commun. (Camb.) 47(1), 2010
PMID: 20862425

AUTHOR UNKNOWN, 0

Kennedy, Inorg. Chem. 24(), 1985

Bencini, Inorg. Chim. Acta 274(), 1998

Mitra, Prog. Inorg. Chem. 22(), 1977

Iwamura, Adv. Phys. Org. Chem. 26(), 1990
Ferromagnetic Coupling through Spin Polarization in a Dinuclear Copper(II) Metallacyclophane.
Fernandez I, Ruiz R, Faus J, Julve M, Lloret F, Cano J, Ottenwaelder X, Journaux Y, Munoz MC., Angew. Chem. Int. Ed. Engl. 40(16), 2001
PMID: 12203642

AUTHOR UNKNOWN, Angew. Chem. 113(), 2001
Targeted synthesis of ferromagnetically coupled complexes with modified 1,3,5-trihydroxybenzene ligands.
Glaser T, Gerenkamp M, Frohlich R., Angew. Chem. Int. Ed. Engl. 41(20), 2002
PMID: 12386859

AUTHOR UNKNOWN, Angew. Chem. 114(), 2002

Longuet-Higgins, J. Chem. Phys. 18(), 1950

Cano, Comments Inorg. Chem. 20(), 1998

Dougherty, Acc. Chem. Res. 24(), 1991
Roles of Bridging Ligand Topology and Conformation in Controlling Exchange Interactions between Paramagnetic Molybdenum Fragments in Dinuclear and Trinuclear Complexes.
Ung VA , Cargill Thompson AM, Bardwell DA, Gatteschi D, Jeffery JC, McCleverty JA, Totti F, Ward MD., Inorg Chem 36(16), 1997
PMID: 11670020

McCleverty, Acc. Chem. Res. 31(), 1998
Trinuclear copper complexes with triplesalen ligands: geometric and electronic effects on ferromagnetic coupling via the spin-polarization mechanism.
Glaser T, Heidemeier M, Strautmann JB, Bogge H, Stammler A, Krickemeyer E, Huenerbein R, Grimme S, Bothe E, Bill E., Chemistry 13(33), 2007
PMID: 17937379
Property-oriented rational design of single-molecule magnets: a C3-symmetric Mn6Cr complex based on three molecular building blocks with a spin ground state of St=21/2.
Glaser T, Heidemeier M, Weyhermuller T, Hoffmann RD, Rupp H, Muller P., Angew. Chem. Int. Ed. Engl. 45(36), 2006
PMID: 16897805

AUTHOR UNKNOWN, Angew. Chem. 118(), 2006

Krickemeyer, Z. Naturforsch. B 65(), 2010
Environmental influence on the single-molecule magnet behavior of [Mn(III)6Cr(III)]3+: molecular symmetry versus solid-state effects.
Hoeke V, Heidemeier M, Krickemeyer E, Stammler A, Bogge H, Schnack J, Postnikov A, Glaser T., Inorg Chem 51(20), 2012
PMID: 23013609

Hoeke, Chem. Sci. 3(), 2012
Structural influences on the exchange coupling and zero-field splitting in the single-molecule magnet [Mn(III)6Mn(III)]3+.
Hoeke V, Heidemeier M, Krickemeyer E, Stammler A, Bogge H, Schnack J, Glaser T., Dalton Trans 41(41), 2012
PMID: 22990419

Hoeke, Eur. J. Inorg. Chem. (), 2013

Theil, Inorg. Chim. Acta 361(), 2008

Feldscher, Sci. China Chem. 55(), 2012
A Mn(III) triplesalen-based 1D pearl necklace: exchange interactions and zero-field splittings in a C3-symmetric Mn(III)6 complex.
Glaser T, Heidemeier M, Theil H, Stammler A, Bogge H, Schnack J., Dalton Trans (1), 2009
PMID: 20023950

Glaser, Compt. Rend. Chim. 10(), 2007

Kemnitz, J. Am. Chem. Soc. 119(), 1997

Fort, J. Am. Chem. Soc. 114(), 1992

Kato, J. Am. Chem. Soc. 105(), 1983

Ovchinnikov, Theor. Chim. Acta 47(), 1978

Dewar, 1969

Glaser, C. R. Chim. 11(), 2008

Glaser, Coord. Chem. Rev. 257(), 2013
Effects of Systematic Variation in Bridging Ligand Structure on the Electrochemical and Magnetic Properties of a Series of Dinuclear Molybdenum Complexes.
Cargill Thompson AM, Gatteschi D, McCleverty JA, Navas JA, Rentschler E, Ward MD., Inorg Chem 35(9), 1996
PMID: 11666494

Ung, Inorg. Chem. 38(), 1999

Bayly, J. Chem. Soc. Dalton Trans. (), 2001
Rational design of an enneanuclear copper(II) complex with a metallacyclophane core.
Ottenwaelder X, Cano J, Journaux Y, Riviere E, Brennan C, Nierlich M, Ruiz-Garcia R., Angew. Chem. Int. Ed. Engl. 43(7), 2004
PMID: 14767956

AUTHOR UNKNOWN, Angew. Chem. 116(), 2004
Ferromagnetic coupling by spin polarization in a trinuclear copper(II) metallacyclophane with a triangular cage-like structure.
Dul MC, Ottenwaelder X, Pardo E, Lescouezec R, Journaux Y, Chamoreau LM, Ruiz-Garcia R, Cano J, Julve M, Lloret F., Inorg Chem 48(12), 2009
PMID: 19402627
Oligo-m-phenyleneoxalamide copper(II) mesocates as electro-switchable ferromagnetic metal-organic wires.
Pardo E, Ferrando-Soria J, Dul MC, Lescouezec R, Journaux Y, Ruiz-Garcia R, Cano J, Julve M, Lloret F, Canadillas-Delgado L, Pasan J, Ruiz-Perez C., Chemistry 16(43), 2010
PMID: 20967904

Dul, Coord. Chem. Rev. 254(), 2010
Ligand design for multidimensional magnetic materials: a metallosupramolecular perspective.
Pardo E, Ruiz-Garcia R, Cano J, Ottenwaelder X, Lescouezec R, Journaux Y, Lloret F, Julve M., Dalton Trans (21), 2008
PMID: 18478138

Foxon, Eur. J. Inorg. Chem. (), 2004
Syntheses, structures, and properties of copper(II) complexes of bis(2-pyridylmethyl) derivatives of o-, m-, and p-phenylenediamine and aniline.
Turba S, Walter O, Schindler S, Nielsen LP, Hazell A, J McKenzie C, Lloret F, Cano J, Julve M., Inorg Chem 47(20), 2008
PMID: 18798612
Substituted m-phenylene bridges as strong ferromagnetic couplers for Cu(II)-bridge-Cu(II) magnetic interactions: new perspectives.
Paital AR, Mitra T, Ray D, Wong WT, Ribas-Arino J, Novoa JJ, Ribas J, Aromi G., Chem. Commun. (Camb.) (41), 2005
PMID: 16228025

Yuste, Inorg. Chim. Acta 363(), 2010

Plaul, Inorg. Chim. Acta 374(), 2011

Plaul, Polyhedron 28(), 2009

Plass, Chem. Unserer Zeit 32(), 1998
A streamlined synthesis of extended thiophloroglucinol ligands and their trinuclear NiII3 complexes.
Feldscher B, Theil H, Stammler A, Bogge H, Glaser T., Dalton Trans 43(10), 2014
PMID: 24457995

Noodleman, Adv. Inorg. Chem. 38(), 1992
Preparation and Characterization of a Diamagnetic Sulfido-Bridged Divanadium Amide Complex.
Moore M, Feghali K, Gambarotta S., Inorg Chem 36(10), 1997
PMID: 11669843

Kahn, 1984

Glaser, J. Am. Chem. Soc. 121(), 1999

Rose, J. Am. Chem. Soc. 121(), 1999

Solomon, Coord. Chem. Rev. 200-202(), 2000
Electron transfer in proteins.
Gray HB, Winkler JR., Annu. Rev. Biochem. 65(), 1996
PMID: 8811189
Iron-sulfur clusters: nature's modular, multipurpose structures.
Beinert H, Holm RH, Munck E., Science 277(5326), 1997
PMID: 9235882

Houser, J. Am. Chem. Soc. 117(), 1995

Houser, J. Am. Chem. Soc. 118(), 1996

Holland, J. Am. Chem. Soc. 121(), 1999

Feldscher, Polyhedron 30(), 2011
Probing the radialene-character in triplesalophen ligands by spectroscopic and structural analysis.
Freiherr von Richthofen CG, Stammler A, Bogge H, Glaser T., J. Org. Chem. 77(3), 2012
PMID: 22225401

Freiherr, Z. Naturforsch. B 68(), 2013

Freiherr, Eur. J. Inorg. Chem. (), 2012

Maas, 1997
Phospharadialenes--a new kid in town.
Hopf H., Angew. Chem. Int. Ed. Engl. 51(48), 2012
PMID: 23081749

AUTHOR UNKNOWN, Angew. Chem. 124(), 2012

Hopf, Angew. Chem. Int. Ed. Engl. 31(), 1992

AUTHOR UNKNOWN, Angew. Chem. 104(), 1992
Highly stable keto-enamine salicylideneanilines.
Chong JH, Sauer M, Patrick BO, MacLachlan MJ., Org. Lett. 5(21), 2003
PMID: 14535719
N-salicylideneanilines: tautomers for formation of hydrogen-bonded capsules, clefts, and chains.
Sauer M, Yeung C, Chong JH, Patrick BO, MacLachlan MJ., J. Org. Chem. 71(2), 2006
PMID: 16408993

Allen, Acta Crystallogr. Sect. B 53(), 1997

Corrigan, Aust. J. Chem. 31(), 1978

Mietrach, Eur. J. Inorg. Chem. (), 2009

Olah, Angew. Chem. Int. Ed. Engl. 19(), 1980

AUTHOR UNKNOWN, Angew. Chem. 92(), 1980

Krinsky, Organometallics 26(), 2007

Andrieu, Org. Magn. Res. 11(), 1978
Hydrogen bonding in Schiff bases--NMR, structural and experimental charge density studies.
Makal A, Schilf W, Kamienski B, Szady-Chelmieniecka A, Grech E, Wozniak K., Dalton Trans 40(2), 2010
PMID: 21109863

Martínez, Eur. J. Org. Chem. (), 2011
Tautomerism in Schiff bases. The cases of 2-hydroxy-1-naphthaldehyde and 1-hydroxy-2-naphthaldehyde investigated in solution and the solid state.
Martinez RF, Avalos M, Babiano R, Cintas P, Jimenez JL, Light ME, Palacios JC., Org. Biomol. Chem. 9(24), 2011
PMID: 22042218
Influence of bond fixation in benzo-annulated N-salicylideneanilines and their ortho-C(=O)X derivatives (X = CH3, NH2, OCH3) on tautomeric equilibria in solution.
Gawinecki R, Kuczek A, Kolehmainen E, Osmialowski B, Krygowski TM, Kauppinen R., J. Org. Chem. 72(15), 2007
PMID: 17590046

Sanz, Tetrahedron 61(), 2005

Schilf, J. Mol. Struct. 743(), 2005

Schilf, J. Mol. Struct. 708(), 2004

Schilf, J. Mol. Struct. 552(), 2000

Dudek, J. Am. Chem. Soc. 86(), 1964

Schilf, J. Mol. Struct. 602-603(), 2002

Goswami, Inorg. Chim. Acta 303(), 2000

Gomes, Dalton Trans. (), 2000
Molecular and electronic structures of one-electron oxidized Ni(II)-(dithiosalicylidenediamine) complexes: Ni(III)-thiolate versus Ni(II)-thiyl radical states.
Stenson PA, Board A, Marin-Becerra A, Blake AJ, Davies ES, Wilson C, McMaster J, Schroder M., Chemistry 14(8), 2008
PMID: 18213560

Yamamura, Chem. Lett. (), 1989

Bosnich, J. Am. Chem. Soc. 90(), 1968

Crawford, Spectrochim. Acta 19(), 1963

Di, J. Am. Chem. Soc. 119(), 1997

Walleck, Inorg. Chim. Acta 363(), 2010

Kruszewski, Tetrahedron Lett. 13(), 1972

Krygowski, J. Chem. Inf. Comput. Sci. 33(), 1993

Allen, J. Chem. Soc. Perkin Trans. (), 1987

Corrigan, Aust. J. Chem. 29(), 1976

Marini, J. Chem. Soc. Dalton Trans. (), 1983
Interplay between hydrogen-bond formation and multicenter pi-electron delocalization: intramolecular hydrogen bonds.
Lenain P, Mandado M, Mosquera RA, Bultinck P., J Phys Chem A 112(42), 2008
PMID: 18821741

Dixit, Tetrahedron 51(), 1995

Fritz, Z. Naturforsch. B 62(), 2007

Feldscher, Eur. J. Inorg. Chem. (), 2013
Non-innocent ligand behavior of a bimetallic Ni Schiff-base complex containing a bridging catecholate.
Dunn TJ, Ramogida CF, Simmonds C, Paterson A, Wong EW, Chiang L, Shimazaki Y, Storr T., Inorg Chem 50(14), 2011
PMID: 21675708

AUTHOR UNKNOWN, 0
A short history of SHELX.
Sheldrick GM., Acta Crystallogr., A, Found. Crystallogr. 64(Pt 1), 2007
PMID: 18156677

AUTHOR UNKNOWN, 0

van, Acta Crystallogr. Sect. A 46(), 1990

AUTHOR UNKNOWN, 0
Erratum: Voltage-dependent scanning-tunneling microscopy of a crystal surface: Graphite
Selloni A, Carnevali P, Tosatti E, Chen CD., Phys. Rev., B Condens. Matter 34(10), 1986
PMID: 9939408

Schäfer, J. Chem. Phys. 100(), 1994

Schäfer, J. Chem. Phys. 97(), 1992
Accurate Coulomb-fitting basis sets for H to Rn.
Weigend F., Phys Chem Chem Phys 8(9), 2006
PMID: 16633586

Eichkorn, Chem. Phys. Lett. 240(), 1995

Eichkorn, Theor. Chem. Acc. 97(), 1997

Cheng, Acta Crystallogr. Sect. E 61(), 2005

Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®

Quellen

PMID: 24976372
PubMed | Europe PMC

Suchen in

Google Scholar