Coordination chemistry of the main group elements with phosphine, arsine and stibine ligands

Burt, Jennifer; Levason, William; Reid, Gillian

doi:10.1016/j.ccr.2013.09.020

Cited by 100 publications

(142 citation statements)

References 349 publications

(402 reference statements)

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“…We wished to establish whether sudden structural changes consistent with a clear distinction between bonding and non‐bonding (repulsive, frustrated) interaction will be observed, or whether smooth trend of P–Sb distances will be produced in the series consistent with a “spectrum‐like” character of the dative interaction. Indeed, differentiation of “primary” and “secondary” coordination in main group chemistry was mentioned by Levason in a recent review as one of the issues in contemporary Main Group chemistry 3b. In this study we provide insight into these interactions using combination of experimental (structural, spectroscopic) and computational approaches.…”

Section: Introductionmentioning

confidence: 87%

Structural, Spectroscopic and Computational Examination of the Dative Interaction in Constrained Phosphine–Stibines and Phosphine–Stiboranes

Chalmers

Bühl

Arachchige

et al. 2015

Chemistry A European J

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A series of phosphine-stibine and phosphine-stiborane peri-substituted acenaphthenes containing all permutations of pentavalent groups -SbCln Ph4-n (5-9), as well as trivalent groups -SbCl2 , -Sb(R)Cl, and -SbPh2 (2-4, R=Ph, Mes), were synthesised and fully characterised by single crystal diffraction and multinuclear NMR spectroscopy. In addition, the bonding in these species was studied by DFT computational methods. The P-Sb dative interactions in both series range from strongly bonding to non-bonding as the Lewis acidity of the Sb acceptor is decreased. In the pentavalent antimony series, a significant change in the P-Sb distance is observed between -SbClPh3 and -SbCl2 Ph2 derivatives 6 and 7, respectively, consistent with a change from a bonding to a non-bonding interaction in response to relatively small modification in Lewis acidity of the acceptor. In the Sb(III) series, two geometric forms are observed. The P-Sb bond length in the SbCl2 derivative 2 is as expected for a normal (rather than a dative) bond. Rather unexpectedly, the phosphine-stiborane complexes 5-9 represent the first examples of the σ(4) P→σ(6) Sb structural motif.

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Section: Introductionmentioning

confidence: 87%

Structural, Spectroscopic and Computational Examination of the Dative Interaction in Constrained Phosphine–Stibines and Phosphine–Stiboranes

Chalmers

Bühl

Arachchige

et al. 2015

Chemistry A European J

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“…[1][2][3] Experimental 119 Sn NMR parameters 3-7 depend on the local co-ordination geometry and share important similarities with those of 207 Pb. 5,6,13 In contrast, tin(IV) species generally exhibit holodirected co-ordination chemistry 11,14,15 with spans under 400 ppm. 5,6,13 In contrast, tin(IV) species generally exhibit holodirected co-ordination chemistry 11,14,15 with spans under 400 ppm.…”

Section: Introductionmentioning

confidence: 99%

Spin–orbit effects on the ¹¹⁹Sn magnetic-shielding tensor in solids: a ZORA/DFT investigation

Alkan

Holmes

Iuliucci

et al. 2016

Phys. Chem. Chem. Phys.

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Periodic-boundary and cluster calculations of the magnetic-shielding tensors of (119)Sn sites in various co-ordination and stereochemical environments are reported. The results indicate a significant difference between the predicted NMR chemical shifts for tin(ii) sites that exhibit stereochemically-active lone pairs and tin(iv) sites that do not have stereochemically-active lone pairs. The predicted magnetic shieldings determined either with the cluster model treated with the ZORA/Scalar Hamiltonian or with the GIPAW formalism are dependent on the oxidation state and the co-ordination geometry of the tin atom. The inclusion of relativistic effects at the spin-orbit level removes systematic differences in computed magnetic-shielding parameters between tin sites of differing stereochemistries, and brings computed NMR shielding parameters into significant agreement with experimentally-determined chemical-shift principal values. Slight improvement in agreement with experiment is noted in calculations using hybrid exchange-correlation functionals.

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“…It remains puzzling that crystallization of the Grignard reagent bis[2,6-bis(diphenylphosphanylmethyl)phenyl]magnesium (2) from THF or from a mixture of THF and DME yielded solvent-free complexes. The Pearson concept of hard and soft acids and bases suggests that the hard magnesium ions prefer the hard ether bases rather than the soft phosphanes [32]. The structure of starting bromo-2,6-bis(diphenylphosphanylmethyl)benzene shows that the diphenylphosphanylmethyl side arms can turn to the side and open a coordination site at the metal center.…”

Section: Theoretical View On Ether and Phosphane Complexes Of Magnesimentioning

confidence: 99%

Reduction of Bromo- and Iodo-2,6-bis(diphenylphosphanylmethyl)benzene with Magnesium and Calcium

Koch

Krieck

Görls

et al. 2016

Preprint

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Arylmagnesium and -calcium reagents are easily accessible, however, ether degradation processes limit the storability especially of the calcium-based heavy Grignard reagents. Ortho-bound substituents with phosphanyl donor sites usually block available coordination sites and stabilize such complexes. The reaction of bromo-2,6-bis(diphenylphosphanylmethyl)benzene (1a) with magnesium in tetrahydrofuran yields [Mg{C6H3-2,6-(CH2PPh2)2}2] (2) after recrystallization from 1,2-dimethoxyethane. However, the similarly performed reduction of bromo- (1a) and iodo-2,6-bis(diphenylphosphanylmethyl)benzene (1b) with calcium leads to ether cleavage and subsequent degradation products. α-Deprotonation of THF yields 1,3-bis(diphenylphosphanylmethyl)benzene. Furthermore, the insoluble THF adducts of dimeric calcium diphenylphosphinate halides, [(thf)3Ca(X)(µ-O2PPh2)]2 [X = Br (3a), I (3b)], precipitate verifying ether decomposition and cleavage of P-C bonds. Ether adducts of calcium halides [such as [(dme)2(thf)CaBr2] (4)] form supporting the initial Grignard reaction and a subsequent Schlenk-type dismutation reaction.

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Coordination chemistry of the main group elements with phosphine, arsine and stibine ligands

Cited by 100 publications

References 349 publications

Structural, Spectroscopic and Computational Examination of the Dative Interaction in Constrained Phosphine–Stibines and Phosphine–Stiboranes

Structural, Spectroscopic and Computational Examination of the Dative Interaction in Constrained Phosphine–Stibines and Phosphine–Stiboranes

Spin–orbit effects on the ¹¹⁹Sn magnetic-shielding tensor in solids: a ZORA/DFT investigation

Reduction of Bromo- and Iodo-2,6-bis(diphenylphosphanylmethyl)benzene with Magnesium and Calcium

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Coordination chemistry of the main group elements with phosphine, arsine and stibine ligands

Cited by 100 publications

References 349 publications

Structural, Spectroscopic and Computational Examination of the Dative Interaction in Constrained Phosphine–Stibines and Phosphine–Stiboranes

Structural, Spectroscopic and Computational Examination of the Dative Interaction in Constrained Phosphine–Stibines and Phosphine–Stiboranes

Spin–orbit effects on the 119Sn magnetic-shielding tensor in solids: a ZORA/DFT investigation

Reduction of Bromo- and Iodo-2,6-bis(diphenylphosphanylmethyl)benzene with Magnesium and Calcium

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Spin–orbit effects on the ¹¹⁹Sn magnetic-shielding tensor in solids: a ZORA/DFT investigation