A Nickel‐Anthracene Complex Having η<sup>3</sup> and η<sup>4</sup> Coordination in One Crystal

Boese, Roland; Stanger, Amnon; Stellberg, Peter; Shazar, Anat

doi:10.1002/anie.199314751

Cited by 41 publications

(22 citation statements)

References 13 publications

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“…The dihedral angle between the al most planar butadiene moiety (the C(1)-C(4) axis devi ates from the plane by 2-3°) and the rest part of the ligand 42 These results suggest that the transition state 1A TS1 has a η 4 structure (Fig. 3) and that the rearrangement is described by the scheme 1A → 1A TS1 → 1C.…”

Section: Methodsmentioning

confidence: 78%

Intra- and inter-ring haptotropic rearrangements in (naphthalene and anthracene)nickel complexes: a DFT study

Oprunenko

Gloriozov

2011

Russ Chem Bull

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Density functional quantum chemical calculations of the mechanisms of metallotropic η 2 ,η 2 intra and η 2 ,η 2 inter ring haptotropic rearrangements (HRs) in 16e zero valent η 2 (naphthalene and anthracene)nickel complexes involving migration of the organometallic group within the same ring or from one aromatic ring to the other were carried out. The structures of the initial complexes, transition states, and intermediates were determined. The intra ring HRs in these systems proceed via low energy η 4 cis butadiene transition states. The inter ring HRs proceed along the periphery of the naphthalene and anthracene ligands via high energy η 3 allylic transition states. In contrast to well investigated η 6 ,η 6 inter ring HRs in (naphthalene and anthracene)tricarbonylchromium complexes, the activation barriers to the η 2 ,η 2 inter ring HRs in the corresponding nickel complexes are much lower. Transition states of these processes are characterized by higher hapticity compared to the initial complexes. This also distinguishes the nickel complexes from the corresponding Cr(CO) 3 complexes for which the hapticities of transition states of the η 6 ,η 6 inter ring HRs are lower than those of the initial complexes. The calculated activation barriers to the η 2 ,η 2 intra ring HRs in the (naphthalene and anthracene)nickel complexes as well as the barrier to rotation of the organonickel group in the naphthalene complex are in good agreement with the experimental data. The calculated barriers to the η 2 ,η 2 inter ring HRs in the naphthalene and anthracene complexes are 3-5 kcal mol -1 lower than the experimental values. This is probably due to the competition between two mechanisms of this process, a low energy intramolecular mechanism and a high energy intermolecular dissociative mechanism.

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Section: Methodsmentioning

confidence: 78%

Intra- and inter-ring haptotropic rearrangements in (naphthalene and anthracene)nickel complexes: a DFT study

Oprunenko

Gloriozov

2011

Russ Chem Bull

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“…The CC bonds of the coordinated “diene” unit of anthracene in 2 (C(29)C(31)=1.384(7) Å, C(29)C(30)=1.394(7) Å, C(30)C(32)=1.401(7) Å) are mildly shorter than the corresponding bonds in the homoleptic anionic complex [Co(η 4 ‐C 14 H 10 ) 2 ] − (1.406(5), 1.424(5), 1.422(5) Å) 5c. Meanwhile, the CoC bond lengths of the outer carbon atoms (av.…”

Section: Resultsmentioning

confidence: 94%

“…These facts indicate that there must be stronger back‐bonding of the metal center in the latter complex than in 2 . In comparison, the analogous iron complex [Fe(η 4 ‐anthracene) 2 ] − shows an even larger back donation, as reflected by the long–short–long, “enediyl” pattern in the coordinated CC bonds of η 4 ‐C 14 H 10 (1.412(3), 1.405(4), 1.416(4) Å),4b which is absent in 2 and [Co(η 4 ‐C 14 H 10 ) 2 ] − 5c…”

Section: Resultsmentioning

confidence: 99%

Mono‐ and Dinuclear Heteroleptic Cobalt Complexes with α‐Diimine and Polyarene Ligands

Wang

Zhao

Gong

et al. 2015

Chemistry A European J

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Reactions of the dimeric cobalt complex [(L(-) Co)2 ] (1, L=[(2,6-iPr2 C6 H3 )NC(Me)]2 ) with polyarenes afforded a series of mononuclear and dinuclear complexes: [LCo(η(4) -anthracene)] (2), [LCo(μ-η(4) :η(4) -naphthalene)CoL] (3), and [LCo(μ-η(4) :η(4) -phenanthrene)CoL] (4). The pyrene complexes [{Na2 (Et2 O)2 }{LCo(μ-η(3) :η(3) -pyrene)CoL}] (5) and [{Na2 (Et2 O)3 }{LCo(η(3) -pyrene)}] (6) were obtained by treating precursor 1 with pyrene followed by reduction with Na metal. These complexes contain three potential redox active centers: the cobalt metal and both α-diimine and polyarene ligands. Through a combination of X-ray crystallography, EPR spectroscopy, magnetic susceptibility measurement, and DFT computations, the electronic configurations of these complexes were studied. It was determined that complexes 2-4 have a high-spin Co(I) center coupled with a radical α-diimine ligand and a neutral polyarene ligand. Whereas, the ligand L in complexes 5 and 6 has been further reduced to the dianion, the cobalt remains in a formal (I) oxidation state, and the pyrene molecule is either neutral or monoanionic.

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“…[ 17] The solution NMR spectroscopic data discussed in Part I indicate the presence of a second quite distinct pyrene isomer, 7B, lying only 0.5 kcal/mol above 7A. Based on the observed 31 P chemical shifts we proposed a structure where the metal was coordinated to one of the inner rings of the pyrene unit.…”

Section: Model Complexes Of Ethene Allyl Anion Butadiene and Benzenementioning

confidence: 97%

{Rh(PiBu₃)₂}⁺ Fragments Ligated to Arenes: From Benzene to Polyaromatic Hydrocarbons, Part II – Computational Analysis of Pathways for Haptotropic Migration

Woolf¹,

Al-Ibadi²,

Chaplin³

et al. 2011

Eur J Inorg Chem

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Density functional theory has been used to probe the structures and solution dynamics of a series of polyaromatic hydrocarbon complexes of the 12-electron fragment {Rh(PiBu 3 ) 2 } + . These studies suggest that the strength of the binding of the metal to the hydrocarbon surface is controlled by the electronic demands of both the metal (16-electron configuration) and ligand (maximum retention of aromaticity). In

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A Nickel‐Anthracene Complex Having η³ and η⁴ Coordination in One Crystal

Abstract: Two independent isomeric molecules in one crystal. This was the surprising result of the X‐ray structural analysis of 1. Both molecules can be considered as representatives of transition states of the η2 ⇇η2 rearrangement that is common in Nio–arene complexes.

Cited by 41 publications

References 13 publications

Intra- and inter-ring haptotropic rearrangements in (naphthalene and anthracene)nickel complexes: a DFT study

Intra- and inter-ring haptotropic rearrangements in (naphthalene and anthracene)nickel complexes: a DFT study

Mono‐ and Dinuclear Heteroleptic Cobalt Complexes with α‐Diimine and Polyarene Ligands

{Rh(PiBu₃)₂}⁺ Fragments Ligated to Arenes: From Benzene to Polyaromatic Hydrocarbons, Part II – Computational Analysis of Pathways for Haptotropic Migration

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A Nickel‐Anthracene Complex Having η3 and η4 Coordination in One Crystal

Abstract: Two independent isomeric molecules in one crystal. This was the surprising result of the X‐ray structural analysis of 1. Both molecules can be considered as representatives of transition states of the η2 ⇇η2 rearrangement that is common in Nio–arene complexes.

Cited by 41 publications

References 13 publications

Intra- and inter-ring haptotropic rearrangements in (naphthalene and anthracene)nickel complexes: a DFT study

Intra- and inter-ring haptotropic rearrangements in (naphthalene and anthracene)nickel complexes: a DFT study

Mono‐ and Dinuclear Heteroleptic Cobalt Complexes with α‐Diimine and Polyarene Ligands

{Rh(PiBu3)2}+ Fragments Ligated to Arenes: From Benzene to Polyaromatic Hydrocarbons, Part II – Computational Analysis of Pathways for Haptotropic Migration

Contact Info

Product

Resources

About

A Nickel‐Anthracene Complex Having η³ and η⁴ Coordination in One Crystal

{Rh(PiBu₃)₂}⁺ Fragments Ligated to Arenes: From Benzene to Polyaromatic Hydrocarbons, Part II – Computational Analysis of Pathways for Haptotropic Migration