Structural assignment of organotin hydrides containing the oxazoline ligand

Matkowska, Dobrochna; Gola, Maciej; Śnieżek, Marcin; Cmoch, Piotr; Stalinski, K.

doi:10.1016/j.jorganchem.2006.09.039

Cited by 13 publications

(11 citation statements)

References 20 publications

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“…The 1 H NMR spectrum of clean 12 (Figure S24) shows a singlet at 6.79 ppm with distinct 117/119 Sn satellites ( 1 J 117 Sn-H = 1938 Hz, 1 J 119 Sn-H = 2028 Hz). These resonances and coupling constants are comparable to other tin hydrides, including 2h [30]. The 119 Sn NMR of 12 reveals a single resonance at −249.5 ppm, (Figure 7, t = 0) similar to that reported for 2g (δ117Sn = −244.5 ppm in toluene-d8).…”

Section: Oxazoline Stannane Dihydridessupporting

confidence: 77%

“…When 7 was reacted with two equivalents of Br 2 (Scheme 4), 10 was obtained in good yield (79%). After solvent removal, a yellow coloured powder remained and 119 Sn NMR (CDCl 3 ) analysis revealed a single resonance (δ = −290.6 ppm), which corresponds closely to the shift reported for 2g (Figure 2, δ 117Sn = −288.5 ppm) [30]. Two unique molecules of compound 4 (designated as 4′, 4″: Figure 4 bottom) were found within the unit cell, both with tin centers adopting a distorted trigonal bipyramidal geometry (τ5 = 0.80; 0.76, respectively).…”

Section: Halogenated Oxazoline Stannanessupporting

confidence: 73%

“…When 7 was reacted with two equivalents of Br2 (Scheme 4), 10 was obtained in good yield (79%). After solvent removal, a yellow coloured powder remained and 119 Sn NMR (CDCl3) analysis revealed a single resonance (δ = −290.6 ppm), which corresponds closely to the shift reported for 2g (Figure 2, δ117Sn = −288.5 ppm) [30]. In tin species with potentially hypercoordinating 2-methoxybenzyl or dimethylaminobenzyl groups, replacement of an alkyl or aryl group for an electronegative atom imparts a downfield shift of the 119 Sn NMR resonance [9].…”

Section: Halogenated Oxazoline Stannanessupporting

confidence: 71%

“…Compound 12 was initially isolated as a colourless viscous oil and requires cooling (−84 • C) to retard decomposition. Staliński et al had also reported an analogous chiral stannane, 2h (Figure 2), shows sensitivity above −20 • C [30]. The thermal sensitivity of 12 was evident when a NMR sample of the compound was quickly (~1 min) prepared in C 6 D 6 ; the solution rapidly changes from colourless to a bright yellow coloured solution, with a precipitate being noted within a few hours.…”

Section: Oxazoline Stannane Dihydridesmentioning

confidence: 92%

“…X-ray crystallography reveals the nitrogen preferentially datively bonding to the tin center over that of the oxygen atom forming a distorted trigonal bipyramidal geometry around Sn with a relatively short Sn-N bond length (2.414 Å) [23]. The Staliński group later published a series of papers detailing organotin complexes bearing similar chiral oxazoline groups (Figure 2: 2a-g, 3a-e) [27][28][29][30]. Evidence of intramolecular Sn-N interactions were probed effectively by 1 H, 13 C, 15 N and 117 Sn NMR spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Oxazoline Stannane Dihydridessupporting

confidence: 77%

Section: Halogenated Oxazoline Stannanessupporting

confidence: 73%

“…When 7 was reacted with two equivalents of Br2 (Scheme 4), 10 was obtained in good yield (79%). After solvent removal, a yellow coloured powder remained and 119 Sn NMR (CDCl3) analysis revealed a single resonance (δ = −290.6 ppm), which corresponds closely to the shift reported for 2g (Figure 2, δ117Sn = −288.5 ppm) [30]. In tin species with potentially hypercoordinating 2-methoxybenzyl or dimethylaminobenzyl groups, replacement of an alkyl or aryl group for an electronegative atom imparts a downfield shift of the 119 Sn NMR resonance [9].…”

Section: Halogenated Oxazoline Stannanessupporting

confidence: 71%

Section: Oxazoline Stannane Dihydridesmentioning

confidence: 92%

Section: Introductionmentioning

confidence: 99%

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

et al. 2020

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Structural Diversity of Coordination Cores in Homoleptic Tetraaryltin(IV) Dioxolane, Aldehyde and Imines: The First Octacoordinated Double Helicate Tetraorganotin(IV) Compound

2013

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Reaction of [2‐{(CH2O)2CH}C6H4]Li with SnCl4 in a 4:1 molar ratio afforded [2‐{(CH2O)2CH}C6H4]4Sn (1), which was deprotected to give [2‐(O=CH)C6H4]4Sn (2). Homoleptic [2‐(RN=CH)C6H4]4Sn [R = Me2NCH2CH2 (3), 2,4,6‐Me3C6H2 (4), PhCH2 (5)] were obtained by condensation of 2 with the corresponding amine either in solution or by using a green, solvent‐free procedure for (imino)arylmetal species. All compounds were characterised by multinuclear NMR spectroscopy and mass spectrometry, and their molecular structures were determined by single‐crystal X‐ray diffraction. In all cases, the C4Sn core is distorted tetrahedral as a result of the combined effects of the intramolecular coordination of the heteroatoms from the organic ligands and the steric impediments imposed by the ligands. The overall coordination around tin was found to be different, that is, coordination numbers from six for 1 and 4, to seven for 3 and 5 and eight for 2. Compound 2 is the first example of a mononuclear tetraorganotin(IV) compound that contains an octacoordinated metal centre with a double helicate topology in the solid state. Multinuclear NMR spectroscopy studies in solutions of CDCl3 are consistent with equivalent organic groups attached to a tetracoordinate tin atom.

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Heptacoordinate Structures of Organotin Halides with Three Phosphine Donors: Halogen‐Substituent Effect on Geometry

et al. 2019

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Structural studies were performed on heptacoordinate compounds of triorganotin halides {(o-Ph 2 P)C 6 H 4 } 3 SnX [X = F (1), Cl (3), Br (4), I (5)] with three phosphine donors. The fluorostannane (1) has an unusual heptacoordinate geometry, in which the three phosphine donors interact with the Sn center around the opposite coordination site of the Sn-F bond (a form). In contrast, the chloro (3) and bromo (4) analogues have highly distorted pentagonal-bipyramidal geometries (b form), while the iodo analogue (5) has a tricapped tetrahedral geometry (c form). Although both b and c forms have two phosphine donors coordinating to the Sn center around the opposite site of the C ipso atoms and one phosphine donor coordinating to [a]

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Structural assignment of organotin hydrides containing the oxazoline ligand

Cited by 13 publications

References 20 publications

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

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

Structural Diversity of Coordination Cores in Homoleptic Tetraaryltin(IV) Dioxolane, Aldehyde and Imines: The First Octacoordinated Double Helicate Tetraorganotin(IV) Compound

Heptacoordinate Structures of Organotin Halides with Three Phosphine Donors: Halogen‐Substituent Effect on Geometry

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