Uncommon cis Configuration of a Metal-Metal Bridging Noninnocent Nindigo Ligand
DSpace at IIT Bombay
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Title |
Uncommon cis Configuration of a Metal-Metal Bridging Noninnocent Nindigo Ligand
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Creator |
MONDAL, P
PLEBST, S RAY, R MOBIN, SM KAIM, W LAHIRI, GK |
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Subject |
DENSITY-FUNCTIONAL THEORY
DIRUTHENIUM COMPLEX ASYMMETRIC HYDROGENATION EXCITATION-ENERGIES NON-INNOCENCE VALENCE RUTHENIUM MOLECULES DINUCLEAR APPROXIMATION |
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Description |
In contrast to several reported coordination compounds of trans-Nindigo ligands [Nindigo = indigo-bis(N-arylimine) = LH2] with one or two six-membered chelate rings involving one indole N and one extracyclic N for metal binding, the new diruthenium complex ion [(acac)(2)Ru(mu,eta(2):eta(2)-L)Ru(bpy)(2)](2+) = 2(2+) exhibits edge-sharing five- and seven-membered chelate rings in the first documented case of asymmetric bridging by a Nindigo ligand in the cis configuration [L2- = indigo-bis(N-phenylimine)dianion]. The dication in compound [2](ClO4)(2) displays one Ru(alpha-diimine)(3) site and one ruthenium center with three negatively charged chelate ligands. Compound [2](ClO4)(2) is obtained from the [Ru(bpy)(2)](2+)-containing cis precursor [(LH)Ru(bpy)(2)]ClO4 = [1]ClO4, which exhibits intramolecular H-bonding in the cation. Four accessible oxidation states each were characterized for the 1(n) and 2(n) redox series with respect to metal- or ligand-centered electron transfer, based on X-ray structures, electron paramagnetic resonance, and ultraviolet-visible-near-infrared spectroelectrochemistry in conjunction with density functional theory calculation results. The structural asymmetry in the Ru-III/Ru-II system 2(2+) is reflected by the electronic asymmetry (class I mixed-valence situation), leaving the noninnocent Nindigo bridge as the main redox-active site.
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Publisher |
AMER CHEMICAL SOC
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Date |
2014-12-28T12:32:50Z
2014-12-28T12:32:50Z 2014 |
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Type |
Article
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Identifier |
INORGANIC CHEMISTRY, 53(17)9348-9356
0020-1669 1520-510X http://dx.doi.org/10.1021/ic501460d http://dspace.library.iitb.ac.in/jspui/handle/100/16540 |
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Language |
English
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