Fluxionality of (.eta.2-naphthalene)(iso-Pr2P(CH2)n-iso-Pr2P)Ni0 (n = 2,3) in the solid state and solution as studied by CP/MAS and 2D carbon-13 NMR spectroscopy

Benn, Reinhard; Mynott, Richard; Topalović, Ivana; Scott, Fred

doi:10.1021/om00112a002

Cited by 59 publications

(82 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This fact is illustrated by strong depen dence of the thermodynamic parameters of haptotropic rearrangements on the aggregation state of the comp lexes. 20 The low ΔG ≠ value for the solution agrees with the activation barriers to the η 2 ,η 2 intra ring HRs in the cyclo polyolefin and arene complexes 8-22 mentioned above (see Scheme 1).…”

Section: Methodssupporting

confidence: 78%

“…cannot be ruled out. 20 In this case, the barrier to the process involving the averaging of the 31 P NMR signals of two different phosphorus atoms ap proaches the barrier to rotation about the double bond in the L 2 Ni fragment in the ethylene complex L 2 Ni(C 2 H 4 ). 39 This provides additional arguments in favor that it is rota tion of the Ni phosphorus metallacycle about the axis per pendicular to the double bond that is responsible for the averaging of the signals of phosphorus atoms in complex 1a.…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

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

Oprunenko

Gloriozov

2011

Russ Chem Bull

View full text Add to dashboard Cite

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.

show abstract

Section: Methodssupporting

confidence: 78%

Section: Methodsmentioning

confidence: 99%

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

Oprunenko

Gloriozov

2011

Russ Chem Bull

View full text Add to dashboard Cite

show abstract

“…For . [8] In contrast, the only system to the best of our knowledge to exhibit fast interring rearrangements is the Ni 0 complex [Ni(h 2 -C 10 H 8 )(dippe)] (dippe 1,2-bis(diisopropylphosphanyl)ethane), [2] for which a DG = of 15 kcal mol À1 was estimated. Presumably, the formally d 10 nickel center does not engage in strong p back-donation to the naphthalene ring, and this facilitates both intra-and interring migration.…”

mentioning

confidence: 99%

Dinuclear π Complexes of Yttrium and Lutetium with Sandwiched Naphthalene and Anthracene Ligands: Evidence for Rapid Intramolecular Inter-Ring Rearrangements

Fryzuk

Jafarpour

Kerton

et al. 2000

Angew. Chem. Int. Ed.

View full text Add to dashboard Cite

“…30 Due to the η 4 configuration of com plexes I-IV, only the η 4 → ← η 4 inter ring haptotropy is possible, whereas the intra ring haptotropy similar to the η 2 → ← η 2 haptotropy in the naphthalene nickel η 2 com plexes is impossible. 6 The DFT study of the structure of these naphthalene nickel complexes, as well as the intra ring (Scheme 5) and inter ring rearrangements (Scheme 6) in these complexes will be published elsewhere.…”

Section: Resultsmentioning

confidence: 99%

“…It is explained by high activa tion barrier to the IHR in question. For instance, no dy namic phenomena were observed in 1 H and 13 C NMR spectra of η 6 acenaphthyleneCr(CO) 3 , 2 η 6 C 10 H 8 Cr(CO) 3 , 3 [(η 6 C 10 H 8 )Ir(C 5 Me 5 )] 2+ (PF 6 -) 2 (70 °C, CF 3 COOH), 4 (η 6 C 10 H 8 ) 2 Cr (130 °C, C 6 D 6 ) 5 samples in the NMR time scale upon heating. Only recently, these effects were detected for the 16 electron nickel complexes of naphth alene (η 2 C 10 H 8 )Ni(Pr 2 NCH 2 CH 2 NPr 2 ) 6 and anthracene (η 2 C 14 H 10 )Ni(PEt 2 ) 2 (η 2 ,η 2 IHR).…”

mentioning

confidence: 99%

Intramolecular inter-ring haptotropic rearrangement in iridium naphthalene complexes: a DFT study

Oprunenko

Gloriozov

2010

Russ Chem Bull

View full text Add to dashboard Cite

Quantum chemical simulation of the inter ring haptotropic rearrangement (IHR) in iridi um naphthalene complexes [η 4 Ir(C 10 H 8 )L 2 ] + (L = PH 3 , PMe 3 , PPh 3 ) involving migration of organometallic group from one of the aromatic ring to the other, was performed using the PBE density functional method with the TZV2p basis set for valence electrons and the relativis tic SBK JC pseudopotentials for the core electrons. The structures of the transition states and intermediates were studied. The IHR proceeds at the periphery of the naphthalene ligand. All transition states have reduced symmetry and hapticity compared with the initial complexes. The calculated thermodynamic parameters of the IHR are in agreement with the NMR data for the related iridium complex of ethylnaphthalene [η 4 Ir(2 ethylnaphthalene)L 2 ] + A -, L = PPh 3 , A = SbF 6 , k ≈ 6•10 -4 s -1 , ΔG ≠ 283 K ≈ 21 kcal mol -1 ).

show abstract

Fluxionality of (.eta.2-naphthalene)(iso-Pr2P(CH2)n-iso-Pr2P)Ni0 (n = 2,3) in the solid state and solution as studied by CP/MAS and 2D carbon-13 NMR spectroscopy

Cited by 59 publications

References 0 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

Dinuclear π Complexes of Yttrium and Lutetium with Sandwiched Naphthalene and Anthracene Ligands: Evidence for Rapid Intramolecular Inter-Ring Rearrangements

Intramolecular inter-ring haptotropic rearrangement in iridium naphthalene complexes: a DFT study

Contact Info

Product

Resources

About