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Syntheses and properties of heterobimetallic ligand-bridged ruthenium(II)/rhenium(I) complexes and their monometallic congeners

Syntheses and properties of heterobimetallic ligand-bridged ruthenium(II)/rhenium(I) complexes and their monometallic congeners
Syntheses and properties of heterobimetallic ligand-bridged ruthenium(II)/rhenium(I) complexes and their monometallic congeners
We have prepared three new heterobimetallic complexes containing electron-donating trans-{RuIICl(pdma)2}+ [pdma = 1,2-phenylenebis(dimethylarsine)] centers linked to electron-deficient fac-{ReI(biq)(CO)3}+ (biq = 2,2?-biquinolinyl) units. The bridging units are 4,4?-bipyridyl (4,4?-bpy), E-1,2-bis(4-pyridyl)ethylene (bpe), or 1,4-bis[E-2-(4-pyridyl)ethenyl]benzene (bpvb) ligands. A number of new monometallic precursor complexes have also been synthesized and fully characterized, primarily for purposes of comparison. The electronic absorption spectra of the bimetallic species are dominated by intense, visible d(RuII) ? ?*(4,4?-bpy/bpe/bpvb) metal-to-ligand charge-transfer (MLCT) bands and d(ReI) ? ?*(biq) absorptions in the near-UV region. Cyclic voltammetric studies reveal both RuIII/II oxidation and ligand-based reduction processes and show no evidence for significant electronic communication between the two metal centers. Stark spectroscopic studies on the visible MLCT bands show that extending the conjugation leads to increases in the dipole moment change and the transition dipole moment, and these changes combine to afford increased static first hyperpolarizabilities, ?0, estimated by using the two-state model. Comparisons with monometallic RuII complexes reveal that methylation of the free pyridyl nitrogen leads to larger ?0 responses than does coordination of the fac-{ReI(biq)(CO)3}+ center. Single-crystal X-ray structures have been determined for solvated adducts of the bimetallic complex salts trans,fac-[RuIICl(pdma)2(?-L?L)ReI(CO)3(biq)](PF6)2 (L?L = 4,4?-bpy or bpe) and also for the monometallic compounds fac-[ReI(biq)(CO)3(L?L)]PF6 (L?L = 4,4?-bpy or bpe) and trans-[RuIICl(pdma)2(L?L)]PF6 [L?L = 2,7-diazapyrene or (E,E)-1,4-bis(4-pyridyl)-1,3-butadiene].
transition-metal-complexes, nonlinear-optical properties, mixed-valency, bimetallic complexes, binuclear complexes, crystal-structures, mononitrosyl redox centers, acceptor groups, charge-transfer, quantum cellular-automata
0276-7333
2730-2742
Coe, Benjamin J.
a31c652b-47a8-4478-8c4c-298a252e6d91
Fitzgerald, Emma C.
b8f8f77b-b249-4bdb-9726-a42f45245aba
Helliwell, Madeleine
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Brunschwig, Bruce S.
9963c670-c36f-476b-83e8-7bba982cbdc6
Fitch, Anthony G.
e13ed6b6-3225-429c-b4fe-3d64a636ef91
Harris, James A.
9cb0084b-5141-4ff4-a69c-3ce4a6d8f5fb
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Coe, Benjamin J.
a31c652b-47a8-4478-8c4c-298a252e6d91
Fitzgerald, Emma C.
b8f8f77b-b249-4bdb-9726-a42f45245aba
Helliwell, Madeleine
974b9c73-cb00-4d9c-87c7-0a2119a95dfc
Brunschwig, Bruce S.
9963c670-c36f-476b-83e8-7bba982cbdc6
Fitch, Anthony G.
e13ed6b6-3225-429c-b4fe-3d64a636ef91
Harris, James A.
9cb0084b-5141-4ff4-a69c-3ce4a6d8f5fb
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da

Coe, Benjamin J., Fitzgerald, Emma C., Helliwell, Madeleine, Brunschwig, Bruce S., Fitch, Anthony G., Harris, James A., Coles, Simon J., Horton, Peter N. and Hursthouse, Michael B. (2008) Syntheses and properties of heterobimetallic ligand-bridged ruthenium(II)/rhenium(I) complexes and their monometallic congeners. Organometallics, 27 (12), 2730-2742. (doi:10.1021/om800105c).

Record type: Article

Abstract

We have prepared three new heterobimetallic complexes containing electron-donating trans-{RuIICl(pdma)2}+ [pdma = 1,2-phenylenebis(dimethylarsine)] centers linked to electron-deficient fac-{ReI(biq)(CO)3}+ (biq = 2,2?-biquinolinyl) units. The bridging units are 4,4?-bipyridyl (4,4?-bpy), E-1,2-bis(4-pyridyl)ethylene (bpe), or 1,4-bis[E-2-(4-pyridyl)ethenyl]benzene (bpvb) ligands. A number of new monometallic precursor complexes have also been synthesized and fully characterized, primarily for purposes of comparison. The electronic absorption spectra of the bimetallic species are dominated by intense, visible d(RuII) ? ?*(4,4?-bpy/bpe/bpvb) metal-to-ligand charge-transfer (MLCT) bands and d(ReI) ? ?*(biq) absorptions in the near-UV region. Cyclic voltammetric studies reveal both RuIII/II oxidation and ligand-based reduction processes and show no evidence for significant electronic communication between the two metal centers. Stark spectroscopic studies on the visible MLCT bands show that extending the conjugation leads to increases in the dipole moment change and the transition dipole moment, and these changes combine to afford increased static first hyperpolarizabilities, ?0, estimated by using the two-state model. Comparisons with monometallic RuII complexes reveal that methylation of the free pyridyl nitrogen leads to larger ?0 responses than does coordination of the fac-{ReI(biq)(CO)3}+ center. Single-crystal X-ray structures have been determined for solvated adducts of the bimetallic complex salts trans,fac-[RuIICl(pdma)2(?-L?L)ReI(CO)3(biq)](PF6)2 (L?L = 4,4?-bpy or bpe) and also for the monometallic compounds fac-[ReI(biq)(CO)3(L?L)]PF6 (L?L = 4,4?-bpy or bpe) and trans-[RuIICl(pdma)2(L?L)]PF6 [L?L = 2,7-diazapyrene or (E,E)-1,4-bis(4-pyridyl)-1,3-butadiene].

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Published date: 2008
Keywords: transition-metal-complexes, nonlinear-optical properties, mixed-valency, bimetallic complexes, binuclear complexes, crystal-structures, mononitrosyl redox centers, acceptor groups, charge-transfer, quantum cellular-automata

Identifiers

Local EPrints ID: 54437
URI: https://eprints.soton.ac.uk/id/eprint/54437
ISSN: 0276-7333
PURE UUID: 1e914f8a-f6a2-48e3-90b4-c3dc34c992da
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for Peter N. Horton: ORCID iD orcid.org/0000-0001-8886-2016

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Date deposited: 06 Aug 2008
Last modified: 07 Aug 2019 00:47

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Contributors

Author: Benjamin J. Coe
Author: Emma C. Fitzgerald
Author: Madeleine Helliwell
Author: Bruce S. Brunschwig
Author: Anthony G. Fitch
Author: James A. Harris
Author: Simon J. Coles ORCID iD
Author: Peter N. Horton ORCID iD

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