Bidentate cycloimidate palladium complexes with aliphatic and aromatic anagostic bonds

Schöler, Stephan; Wahl, Maike H.; Wurster, Nicole I. C.; Puls, Arik; Hättig, Christof; Dyker, Gerald

doi:10.1039/c4cc01060d

Cited by 28 publications

(14 citation statements)

References 30 publications

(38 reference statements)

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“…What was unanticipated is that in the parent DPEphos–H complex such interactions are also present – albeit only observed at very low temperature in solution. Similar properties (C–H⋯M, 2.23–3.01 Å, low-field chemical shifts and apical approaches of C–H groups to d 8 metal centres), have been discussed by others, including: Bergman, 44 Dyker, 42 Fairlamb, 45 and Sabo-Etienne, 38 Fig. 7 .…”

Section: Resultssupporting

confidence: 71%

“…Such demarcations are not always clear-cut, however, as axial sites can also display Lewis-acidic character. 29,41 While with hindsight it is not surprising that the most sterically bulky ligand, DPEphos-i Pr, enforces an anagostic interaction at room temperature, the presence of both aryl and, rarer, 42,43 alkyl anagostic interactions in 2-Me is perhaps more notable. What was unanticipated is that in the parent DPEphos-H complex such interactions are also present -albeit only observed at very low temperature in solution.…”

Section: Variable Temperature Solution Nmr Spectroscopy and The Identification Of Anagostic Interactions In Solution And Solid-statementioning

confidence: 99%

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Ortho-aryl substituted DPEphos ligands: rhodium complexes featuring C–H anagostic interactions and B–H agostic bonds

et al. 2021

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Section: Resultssupporting

confidence: 71%

Section: Variable Temperature Solution Nmr Spectroscopy and The Identification Of Anagostic Interactions In Solution And Solid-statementioning

confidence: 99%

Ortho-aryl substituted DPEphos ligands: rhodium complexes featuring C–H anagostic interactions and B–H agostic bonds

et al. 2021

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“…Yield: 4.75 g, 75.2%. NMR data ( 1 H, 13 C) matches reported literature data within experimental error [53].…”

Section: Computational Detailssupporting

confidence: 81%

Preparation and DFT Studies of κ2C,N-Hypercoordinated Oxazoline Organotins: Monomer Constructs for Stable Polystannanes

et al. 2020

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Tetraorganotin tin(IV) compounds containing a flexible or rigid (4: Ph3Sn-CH2-C6H4-R; 7: Ph3SnC6H4-R, R = 2-oxazolinyl) chelating oxazoline functionality were prepared in good yields by the reaction of lithiated oxazolines and Ph3SnCl. Reaction of 7 with excess HCl resulted in the isolation of the tin monochlorido compound, 9 (ClSn[Ph2]C6H4-R). Conversion of the triphenylstannanes 7 and 4 into their corresponding dibromido species was successfully achieved from the reaction with Br2 to yield 10 (Br2Sn[Ph]C6H4-R) and 11 (Br2Sn[Ph]-CH2-C6H4-R), respectively. X-ray crystallography of 4, 7, 9, 10, and 11 reveal that all structures adopt a distorted trigonal bipyramidal geometry around Sn in the solid state. Compound 4, with an additional methylene spacer group, displays a comparatively long Sn–N bond distance compared to the dibromido tin species, 11. Several DFT methods were compared for accuracy in predicting the solid-state geometries of compounds 4, 7, 9–11. Compounds 10 and 11 were further converted into the corresponding dihydrides (12: H2Sn[Ph]C6H4-R, 13: H2Sn[Ph]-CH2-C6H4-R), via Br–H exchange, in high yield by reaction with NaBH4. Polymerization of 12 or 13 with a late transition metal catalyst produced a low molecular weight polystannane (14: –[Sn[Ph]C6H4-R]n–, Mw = 10,100 Da) and oligostannane (15: –[Sn[Ph]-CH2-C6H4-R]n–, Mw = 3200 Da), respectively.

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“…The complex thus has anagostic hydrogen atoms above and below the coordination plane. This situation has recently been identified by X‐ray crystallography in complexes containing more rigid ligands than in the present case where on coordination hydrogen atoms are forced to occupy above and below‐plane sites 28…”

Section: Resultsmentioning

confidence: 55%

Steric and Electronic Manipulation of the Anagostic Interaction in 1‐Tetralone Oxime and Imine Complexes of Rhodium(I)

et al. 2015

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Structures and properties for the complexes [RhCl(CO) 2 (L)] (L = 1-tetralone oximes and imines) containing anagostic C-H separations were obtained from density functional calculations using the dispersion corrected PBE-D3 functional. Bench-top syntheses were carried out for several complexes to obtain NMR spectral comparisons. The calculations show a ligand (N)-OH group positions the anagostic hydrogen (H 8 ) more over the metal and (N)-OCMe 3 and (N)-CMe 3 groups more out towards the chloro ligand where weak H···Cl bonding is involved. This positioning is a result of varying Rh-N bond lengths and steric factors arising below the coordination plane where methyl-group H atoms can form additional anagostic approaches to the metal and weak hydrogen bonds with the chloro ligand. QTAIM analysis indicates weak electrostatic repul- [a] Density functional theory (DFT) calculations using the dispersion corrected PBE-D3 hybrid functional (see the computational section for details) were used to obtain structures for the rhodium complexes [RhCl(CO) 2 (L)] (L = 1-tetralone oxime and imine derivatives) where the ligand aromatic ring sits above the coordination plane (Scheme 1). In general these types of complexes are stable entities in which the Cl ligand is not easily removed and as cyclometallation does then not proceed they are ideal for the study of anagostic interactions. [15] Our preliminary stud-Eur.

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Bidentate cycloimidate palladium complexes with aliphatic and aromatic anagostic bonds

Abstract: Palladium(II) complexes of bidentate cycloimidate ligand systems with a triarylmethyl moiety exhibit exceptional downfield shifts in proton NMR spectra due to rare anagostic interactions.

Cited by 28 publications

References 30 publications

Ortho-aryl substituted DPEphos ligands: rhodium complexes featuring C–H anagostic interactions and B–H agostic bonds

Ortho-aryl substituted DPEphos ligands: rhodium complexes featuring C–H anagostic interactions and B–H agostic bonds

Preparation and DFT Studies of κ2C,N-Hypercoordinated Oxazoline Organotins: Monomer Constructs for Stable Polystannanes

Steric and Electronic Manipulation of the Anagostic Interaction in 1‐Tetralone Oxime and Imine Complexes of Rhodium(I)

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