2018
DOI: 10.1080/02603594.2018.1467315
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All That Glitters Is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d10 Metal Centers—A Tribute to Al Cotton on the Tenth Anniversary of His Passing

Abstract: As the tenth year that follows the premature passing of the inorganic chemistry legend F. Albert (Al) Cotton comes to a close, we provide some soul food that we believe Al would have enjoyed as he looks down upon two generations of disciples, a grandchild and two great grandchildren, in his scientific family tree. This article also represents a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that nonetheless pr… Show more

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Cited by 13 publications
(16 citation statements)
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“…may be assigned as strong metal-metal interactions arising from strong metallophilicity and/or polar covalency. 18,22,41 Such a situation corresponds to opposite p-acid/p-base properties of the two metal atoms and nine-membered rings, which agrees with the green-blue spike (sign(l 2 )r z À0.017 a.u.) in Fig.…”
Section: Chemical Science Edge Articlesupporting
confidence: 65%
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“…may be assigned as strong metal-metal interactions arising from strong metallophilicity and/or polar covalency. 18,22,41 Such a situation corresponds to opposite p-acid/p-base properties of the two metal atoms and nine-membered rings, which agrees with the green-blue spike (sign(l 2 )r z À0.017 a.u.) in Fig.…”
Section: Chemical Science Edge Articlesupporting
confidence: 65%
“…Tz)] 3 , blue regions) during the stacking process and quite small formation energies of $3 kcal mol À1 . Notwithstanding the small magnitude of each constituent force, the overall dimer-of-trimer stabilization magnitude of $65 kcal mol À1 herein is even stronger than those in literature precedents of largely undisputed intermolecular covalent bonds, such as those in d 1 -d 1 or d 9 -d 9 ground-state single bonds, 3 P g or 3 S u + excited-state single bonds in the Hg 2 excimer, or singlet (or triplet) p-stacked pyrene 2 sandwiched excimersall of which attain D e values in the #50 kcal mol À1 range 41,[46][47][48][49][50][51]. The stabilization herein is likewise $2Â higher than that in the claimed polar-covalent bonding reported recently in a heterobimetallic Au 2 CuIm 2 Pz complex (D e ¼ $35-40 kcal mol À1 ).…”
mentioning
confidence: 65%
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“…65 Indeed, this lies in the vicinity of bond distances recently scrutinized by Otten et al to be covalent as opposed to cuprophilic. 69 However, we suspect the situation herein to be more similar to the "control" cases in that work whereby the short Cu(I)Cu(I) distances are brought about by the ligand bite size as opposed to covalency, akin to Cotton's classic work on bis(formamidinate) dinuclear adducts, 70 as the situation does not warrant intershell mixing of 4s 0 /4p 0 orbitals with 3d 10 orbitals that is required for covalency.…”
Section: ■ Introductionmentioning
confidence: 99%
“…. Au(I) interactions in a large number of compounds and termed aurophilicity by Pykkö and others [422][423][424][425][426][427]. In gold compounds, the aurophilic interaction is typified by Au .…”
Section: When Is a Bond Not A Bond?mentioning
confidence: 99%