Electronic Communication through Unsaturated Hydrocarbon Bridges in Homobimetallic Organometallic Complexes

Aguirre-Etcheverry, Paulina; O’Hare, Dermot

doi:10.1021/cr9003852

Cited by 317 publications

(272 citation statements)

References 227 publications

Supporting

Mentioning

264

Contrasting

Unclassified

Order By: Relevance

“…No urea-tape structure can be discerned in the crystal packing, possibly inhibited by the steric hindrance of four pyridine groups. The reaction conditions used to transform 5 into the di-Ru complex 6(PF 6 ) 2 are not believed to change the linear conformation.…”

Section: Resultsmentioning

confidence: 99%

“…The former relies on the orbital overlap between the redox termini and the bridging ligand. [2,3] The latter is a result of the charge sharing between/among closely spaced redox components.…”

Section: Introductionmentioning

confidence: 99%

“…[2][3][4] Most MV compounds involve either throughbond or through-space coupling. It remains a challenge to realize both pathways in a single system.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Conformation‐Determined Through‐Bond versus Through‐Space Electronic Communication in Mixed‐Valence Systems with a Cross‐Conjugated Urea Bridge

Gong

Zhong

Yao

2014

Chemistry A European J

View full text Add to dashboard Cite

Bis-triarylamine 2 and cyclometalated diruthenium 6(PF6)2 with a linear trans,trans-urea bridge have been prepared, together with the bis-triarylamine 3 and cyclometalated diruthenium 8(PF6)2 with a folded cis,cis-N,N-dimethylurea bridge. The linear or folded conformations of these molecules are supported by single-crystal X-ray structures of 2, 3, and other related compounds. These compounds display two consecutive anodic redox waves (N(·+/0) or Ru(III/II) processes) with a potential separation of 110-170 mV. This suggests that an efficient electronic coupling is present between two redox termini through the cross-conjugated urea bridge. The degree of electronic coupling has been investigated by using spectroelectrochemical measurements. Distinct intervalence charge-transfer (IVCT) transitions have been observed for mixed-valent (MV) compounds with a linear conformation. The IVCT transitions can also be identified for the folded MV compounds, albeit with a much weaker intensity. DFT results support that the electronic communication occurs by a through-bond and through-space pathway for the linear and folded compounds, respectively. The IVCT transitions of the MV compounds have been reproduced by TDDFT calculations. For the purpose of comparison, a bistriarylamine and a diruthenium complex with an imidazolidin-2-one bridge and a urea-containing mono-triarylamine and monoruthenium complex have been synthesized and studied.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Conformation‐Determined Through‐Bond versus Through‐Space Electronic Communication in Mixed‐Valence Systems with a Cross‐Conjugated Urea Bridge

Gong

Zhong

Yao

2014

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…[1][2][3][4] The synthesis of polymers which contain metallocene units in close proximity is highly desirable as it should allow extended metal-metal interactions throughout the chain, which may result in novel electronic, magnetic or other physical properties. [5] The aromatic ligand pentalene (Pn, C8H6) has shown ability to delocalise electron density between metal centres in anti-bimetallic transition metal compounds, and promote coupling effects through the planar π-system of the bridging Pn ligand.…”

Section: Introductionmentioning

confidence: 99%

Complexes of iron(II) with silylated pentalene ligands; building blocks for homo- and heterobimetallics

et al. 2016

View full text Add to dashboard Cite

(2016) Complexes of Iron(II) with silylated pentalene ligands; building blocks for homo-and heterobimetallics. Polyhedron, This version is available from Sussex Research Online: http://sro.sussex.ac.uk/59846/ This document is made available in accordance with publisher policies and may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the URL above for details on accessing the published version. Copyright and reuse:Sussex Research Online is a digital repository of the research output of the University.Copyright and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable, the material made available in SRO has been checked for eligibility before being made available.Copies of full text items generally can be reproduced, displayed or performed and given to third parties in any format or medium for personal research or study, educational, or not-for-profit purposes without prior permission or charge, provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. DFT calculations on model mono-Fe(η 5 -Pn) compounds reveal the charge densities on the uncoordinated carbon atoms of the pentalene ligand, and hence the potential for incorporating these units into heteronuclear bimetallic complexes is assessed.

show abstract

“…These systems are ideal candidates for the study of intramolecular electron transfer processes [5][6][7], which in turn underpin applications in catalysis [8], energy science [9, 10] and molecular electronics [11,12] whilst also illustrating fine details of electronic structure arising from the often unexpected redox activity of the supporting or bridging ligands [13][14][15][16][17]. Whilst the considerable majority of studies in this area have focussed on bis(monometallic) complexes in which two metal centres are linked through a (usually -conjugated) bridging ligand [18,19], systems derived from organic electrophores [20] and cluster systems [21] have not been overlooked.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure and Electrochemical Properties of Triarylamine Bridged Dicobaltdicarbon Tetrahedrane Clusters

et al. 2012

View full text Add to dashboard Cite

. (2012) 'Synthesis, structure and electrochemical properties of triarylamine bridged dicobaltdicarbon tetrahedrane clusters.', Journal of custer science., 23 (3). 853-872 . Further information on publisher's website:http://dx.doi.org/10.1007/s10876-012-0482-y Publisher's copyright statement:The original publication is available at www.springerlink.com Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. AbstractThe reaction of [Co 2 (CO) 6 (dppm)] (1) + with respect to disproportionation can be attributed to electrostatic effects.

show abstract

Electronic Communication through Unsaturated Hydrocarbon Bridges in Homobimetallic Organometallic Complexes

Cited by 317 publications

References 227 publications

Conformation‐Determined Through‐Bond versus Through‐Space Electronic Communication in Mixed‐Valence Systems with a Cross‐Conjugated Urea Bridge

Conformation‐Determined Through‐Bond versus Through‐Space Electronic Communication in Mixed‐Valence Systems with a Cross‐Conjugated Urea Bridge

Complexes of iron(II) with silylated pentalene ligands; building blocks for homo- and heterobimetallics

Synthesis, Structure and Electrochemical Properties of Triarylamine Bridged Dicobaltdicarbon Tetrahedrane Clusters

Contact Info

Product

Resources

About