Synthesis and coordinating properties of the facultative Sb2O- and As2O-donor ligands O{(CH2)2ER2}2 (E=Sb or As; R=Ph or Me)

Davis, Martin F.; Jura, Marek; Levason, William; Reid, Gillian; Webster, Michael

doi:10.1016/j.jorganchem.2007.08.034

Cited by 11 publications

(13 citation statements)

References 29 publications

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“…The 1 H NMR spectra of ( 1) and ( 2) are consistent with the structures, the most notable features being the SbMe protons which are observed at around 1 ppm-typical of SbMe groups in related compounds. 15,17, 19 The 13 C{ 1 H} NMR spectra are also consistent with the structures showing the highly shielded d(SbMe) at 1.2 and -1.3 ppm, respectively. 4) is attributed in part to the cis-directing influence (preorganisation) of the o-phenylene groups in the backbone.…”

Section: Ligandssupporting

confidence: 69%

“…We have also reported the preparations of the potentially tridentate O(CH 2 CH 2 SbR 2 ) 2 (R = Me or Ph), which behave as bidentate Sb 2 -donor chelates to Cu(I), Ag(I) (structural evidence for both), Rh(III) and Pt(II). 19 A small number of potentially tetradentate Sb 2 N 2 -donor analogues have been described briefly, but no metal complexes are known. 20 We report here the preparation and characterisation of a series of new stibine ligands involving mixed Sb/N-donor sets and both cyclic and open-chain structures, utilising 'pre-organised' reagents to aid cyclisation and to promote chelation.…”

Section: Introductionmentioning

confidence: 99%

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Preparation and properties of cyclic and open-chain Sb/N-donor ligands

et al. 2009

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The preparations of both open-chain and cyclic mixed-donor Sb/N ligands, MeN(CH2-2-C6H4)2SbMe (1), MeN(CH2-2-C6H4SbMe2)2 (2), CH2{CH2N(Me)CH2-2-C6H4SbMe2}2 (3) and CH2{CH2N(Me)CH2-2-C6H4}2SbMe (4), are described via reaction of chlorostibines with dilithio-reagents, and their spectroscopic properties established. Air-stable stibonium derivatives of (3) and (4) have been isolated by treatment of the compounds with excess MeI, which leads to quaternisation at the Sb atoms exclusively. A crystal structure of a bis(stibonium) derivative of (3), [CH2{CH2N(Me)CH2-2-C6H4SbMe3}2]I2, reveals hypervalency at Sb through long-range Sb...N interactions (ca. 2.87 A), giving pseudo-five-membered rings fused to the aromatic rings, and distorted trigonal bipyramidal coordination at Sb. The coordinating properties of compounds (1) to (4) have been investigated through their reactions with Cu(I), Mn(I), Mo(0) and Pt(IV) reagents, and for (1) and (4) by reaction with Fe(0), giving [Fe(CO)4(L)]. The spectroscopic data (IR, 1H, 13C{1H}, 55Mn, 63Cu, 95Mo and 195Pt NMR), mass spectrometry and microanalyses for this series of complexes confirm that coordination occurs via the Sb donor atoms in all cases, with N-coordination only present in fac-[Mn(CO)3(2)](CF3SO3). Crystal structures of [Cu(2)2]BF4, [Mo(CO)4(2)] and [PtMe3I(2)] confirm the coordination modes, showing (2) functioning as a wide-angle bidentate distibine. The structures also show the amine N-donor atoms in the complexes are involved in a hypervalent SbN interaction (ca. 3.0 A) with one of the coordinated Sb atoms in each ligand, leading to significant differences in the conformations of the carbon backbones linking the Sb and N atoms. Reaction of Na3[RhCl6].12H2O with one mol equiv. of (2), (3) or (4) leads to the bis-ligand complex [RhCl2(2)2]Cl and the 1 : 1 Rh : L complexes [RhCl2(3)]Cl and [RhCl3(4)], both of which involve coordination via the Sb and N donor atoms.

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Section: Ligandssupporting

confidence: 69%

Section: Introductionmentioning

confidence: 99%

Preparation and properties of cyclic and open-chain Sb/N-donor ligands

et al. 2009

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“…22 19 The analogous arsine complex is structurally very similar, and is a rare example of intramolecular contacts of this type being formed with the less Lewis acidic As centre, possibly an indication that the effects of crystal packing or optimisation of backbone geometry play a role in directing the position of the O donor atom with respect to the heavy atom in these complexes. 19 In some complexes of these ligands, 'hypervalent' interactions are not obviously present, and the factors governing their formation are too subtle to be easily predictable at the Sb centres and close enough to neither to form a significant interaction (3.643(6) and 3.467(6) Å).…”

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confidence: 99%

“…19,20,21 These were originally of interest as ligands which could present a mixed donor set to a transition metal fragment, allowing examination of stibine coordination within a more robust, chelating ligand framework. As part of this work, complexes with low-valent metal carbonyls were pursued as appropriate acceptors for the soft stibine donors.…”

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Neutral organoantimony(III) and organobismuth(III) ligands as acceptors in transition metal complexes – Role of substituents and co-ligands

Benjamin

Reid

2015

Coordination Chemistry Reviews

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“…23 The tetraselenoether macrocycle [14]aneSe 4 also undergoes elimination of the dimethylene linkages quite readily, 7 and in our recent work we have shown that the related dimethylenelinked As 2 O-donor ligand O(CH 2 CH 2 AsMe 2 ) 2 readily undergoes C-O and C-As scission (this is not observed for the Ph-substituted analogue). 24 A 77 Se{ 1 H} resonance at 148.2 ppm is consistent with formation of some L 4 , however this was a minor product which proved very difficult to separate by column chromatography. Hence this route was not pursued further.…”

Section: Table 2 Selected Bond Lengths (A ˚) and Angles (mentioning

confidence: 82%

Selenoether macrocyclic chemistry—syntheses and properties of new potentially tridentate and hexadentate Se/O-donor macrocycles

et al. 2008

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Treatment of O(CH2CH2SeCN)2 with Na in NH3(l), followed by dropwise addition of a thf solution of o-C6H4(CH2Br)2 at -40 degrees C leads to formation of three mixed Se/O-donor macrocycles which are separable by column chromatography, the [1 + 1] species L1, the [2 + 2] ring L2 and the [3 + 3] ring L3, of which L2 is by far the major species. Using the same starting materials, but in a high dilution cyclisation at room temperature with NaBH4 in thf/EtOH gives exclusively the [1 + 1] ring, L1. The saturated ring Se/O-donor macrocycles, L4 and L5 are obtained by simultaneous dropwise addition of solutions of O(CH2CH2SeCN)2 and Br(CH2)3Br to NaBH4 suspended in thf/EtOH. The small tridentate Se2O-donor ring, L4, is again the dominant product under these conditions (71%), although the more flexible precursors in this reaction also give rise to the larger Se4O2-donor ring, L5, as a by-product in 8% yield. These compounds are readily separated and purified by column chromatography (ethyl acetate:hexane, 1:19). The new macrocycles have been characterised by 1H, (13)C{1H} and (77)Se{1H} NMR spectroscopy and mass spectrometry, together with crystal structures of L1 and L2. Complexes of L1 and L2 with late transition metals (Pd(II), Pt(II), Cu(I) and Ag(I)) are also described.

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Synthesis and coordinating properties of the facultative Sb2O- and As2O-donor ligands O{(CH2)2ER2}2 (E=Sb or As; R=Ph or Me)

Cited by 11 publications

References 29 publications

Preparation and properties of cyclic and open-chain Sb/N-donor ligands

Preparation and properties of cyclic and open-chain Sb/N-donor ligands

Neutral organoantimony(III) and organobismuth(III) ligands as acceptors in transition metal complexes – Role of substituents and co-ligands

Selenoether macrocyclic chemistry—syntheses and properties of new potentially tridentate and hexadentate Se/O-donor macrocycles

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