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Gillian Reid - One of the best experts on this subject based on the ideXlab platform.
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Sodium thioether Macrocyclic Chemistry: remarkable homoleptic octathia coordination to Na+
Inorganic chemistry, 2015Co-Authors: Martin J. D. Champion, John M. Dyke, William Levason, Mark E. Light, David Pugh, Hanusha Bhakhoa, Lydia Rhyman, Ponnadurai Ramasami, Gillian ReidAbstract:Unprecedented homoleptic octathioether Macrocyclic coordination to Na+ in [Na([24]aneS8)]+ has been achieved by using Na[B{3,5-(CF3)2-C6H3}4] as a source of “naked” Na+ ions and confirmed crystallographically, with d(Na–S) = 2.9561(15)–3.0524(15) A. Density functional theory calculations show that there is electron transfer from the S 3p and C 2p valence orbitals of the ligand to the 3s and 3p orbitals of the Na+ ion upon complexation.
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sodium thioether Macrocyclic Chemistry remarkable homoleptic octathia coordination to na
Inorganic Chemistry, 2015Co-Authors: Martin J. D. Champion, John M. Dyke, William Levason, Mark E. Light, David Pugh, Hanusha Bhakhoa, Lydia Rhyman, Ponnadurai Ramasami, Gillian ReidAbstract:Unprecedented homoleptic octathioether Macrocyclic coordination to Na+ in [Na([24]aneS8)]+ has been achieved by using Na[B{3,5-(CF3)2-C6H3}4] as a source of “naked” Na+ ions and confirmed crystallographically, with d(Na–S) = 2.9561(15)–3.0524(15) A. Density functional theory calculations show that there is electron transfer from the S 3p and C 2p valence orbitals of the ligand to the 3s and 3p orbitals of the Na+ ion upon complexation.
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selenoether Macrocyclic Chemistry syntheses and ligand properties of new small ring se3 and se2n donor macrocycles
Dalton Transactions, 2009Co-Authors: William Levason, Gillian Reid, Joanna M. Manning, Matthew Tuggey, Michael WebsterAbstract:Simultaneous dropwise addition of thf/EtOH solutions of Se{(CH2)3OTs}2 and o-C6H4(CH2SeCN)2 or NCSe(CH2)3SeCN to a suspension of NaBH4 in thf/EtOH at room temperature yields gram quantities of the 13- and 12-membered triselenoether macrocycles L1 and L2 respectively in high yield. The 11-membered ring L3 is obtained similarly by simultaneous dropwise addition of thf/EtOH solutions of Na2[o-C6H4Se2] (itself prepared by NaBH4reduction of the polymeric [o-C6H4Se2]n) and Se{(CH2)3OTs}2 to a suspension of NaBH4 in thf/EtOH. The small-ring, potentially tridentate Se2N(pyridyl)-donor macrocycles L4 and L5 were obtained in essentially quantitative yield by simultaneous dropwise addition of thf/EtOH solutions of 2,6-bis(bromomethyl)pyridine and either o-C6H4(CH2SeCN)2 or NCSe(CH2)3SeCN to a suspension of NaBH4 in thf/EtOH at room temperature. L1–L5 have been characterised by 1H, 13C{1H} and 77Se{1H} NMR spectroscopy, EI MS, and for L1 and L4, by X-ray crystal structures. Reaction of PtMe3I with one mol. equiv. of L (L = L1–L5) in refluxing CHCl3 gives the ionic complexes [PtMe3(L)]I cleanly and in good yield. These were characterised by 1H, 13C{1H}, 77Se{1H} and 195Pt NMR spectroscopy, electrospray MS, microanalyses and by crystal structures of [PtMe3(L1)]I and [PtMe3(L4)]I, which confirm distorted octahedral coordination at Pt(IV), with fac-tridentate coordination of the macrocycle in all cases, with anionic iodide. The complexes [PtCl2(L)] (L = L1–L3) were obtained as poorly soluble yellow-orange solids by reaction of PtCl2 with L in MeCN solution. The d3Cr(III) complexes of L (L = L1–L5) were obtained by reaction with [CrCl3(thf)3] in anhydrous CH2Cl2 as distorted octahedral fac-[CrCl3(L)], as poorly soluble blue-purple through to green powdered solids, which have been characterised by microanalysis, UV-visible and IR spectroscopy and by their magnetic moments. The properties of these complexes are compared with related chalcogenoether complexes from the literature involving thioether and acyclic selenoether coordination.
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Selenoether Macrocyclic Chemistry–syntheses and ligand properties of new small-ring Se3- and Se2N-donor macrocycles
Dalton transactions (Cambridge England : 2003), 2009Co-Authors: William Levason, Gillian Reid, Joanna M. Manning, Matthew Tuggey, Michael WebsterAbstract:Simultaneous dropwise addition of thf/EtOH solutions of Se{(CH2)3OTs}2 and o-C6H4(CH2SeCN)2 or NCSe(CH2)3SeCN to a suspension of NaBH4 in thf/EtOH at room temperature yields gram quantities of the 13- and 12-membered triselenoether macrocycles L1 and L2 respectively in high yield. The 11-membered ring L3 is obtained similarly by simultaneous dropwise addition of thf/EtOH solutions of Na2[o-C6H4Se2] (itself prepared by NaBH4reduction of the polymeric [o-C6H4Se2]n) and Se{(CH2)3OTs}2 to a suspension of NaBH4 in thf/EtOH. The small-ring, potentially tridentate Se2N(pyridyl)-donor macrocycles L4 and L5 were obtained in essentially quantitative yield by simultaneous dropwise addition of thf/EtOH solutions of 2,6-bis(bromomethyl)pyridine and either o-C6H4(CH2SeCN)2 or NCSe(CH2)3SeCN to a suspension of NaBH4 in thf/EtOH at room temperature. L1–L5 have been characterised by 1H, 13C{1H} and 77Se{1H} NMR spectroscopy, EI MS, and for L1 and L4, by X-ray crystal structures. Reaction of PtMe3I with one mol. equiv. of L (L = L1–L5) in refluxing CHCl3 gives the ionic complexes [PtMe3(L)]I cleanly and in good yield. These were characterised by 1H, 13C{1H}, 77Se{1H} and 195Pt NMR spectroscopy, electrospray MS, microanalyses and by crystal structures of [PtMe3(L1)]I and [PtMe3(L4)]I, which confirm distorted octahedral coordination at Pt(IV), with fac-tridentate coordination of the macrocycle in all cases, with anionic iodide. The complexes [PtCl2(L)] (L = L1–L3) were obtained as poorly soluble yellow-orange solids by reaction of PtCl2 with L in MeCN solution. The d3Cr(III) complexes of L (L = L1–L5) were obtained by reaction with [CrCl3(thf)3] in anhydrous CH2Cl2 as distorted octahedral fac-[CrCl3(L)], as poorly soluble blue-purple through to green powdered solids, which have been characterised by microanalysis, UV-visible and IR spectroscopy and by their magnetic moments. The properties of these complexes are compared with related chalcogenoether complexes from the literature involving thioether and acyclic selenoether coordination.
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selenoether Macrocyclic Chemistry syntheses and properties of new potentially tridentate and hexadentate se o donor macrocycles
Dalton Transactions, 2008Co-Authors: William Levason, Gillian Reid, Joanna M. Manning, Manisha Nirwan, Raju Ratnani, Hayley Smith, Michael WebsterAbstract: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 °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, 13C{1H} and 77Se{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.
William Levason - One of the best experts on this subject based on the ideXlab platform.
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Sodium thioether Macrocyclic Chemistry: remarkable homoleptic octathia coordination to Na+
Inorganic chemistry, 2015Co-Authors: Martin J. D. Champion, John M. Dyke, William Levason, Mark E. Light, David Pugh, Hanusha Bhakhoa, Lydia Rhyman, Ponnadurai Ramasami, Gillian ReidAbstract:Unprecedented homoleptic octathioether Macrocyclic coordination to Na+ in [Na([24]aneS8)]+ has been achieved by using Na[B{3,5-(CF3)2-C6H3}4] as a source of “naked” Na+ ions and confirmed crystallographically, with d(Na–S) = 2.9561(15)–3.0524(15) A. Density functional theory calculations show that there is electron transfer from the S 3p and C 2p valence orbitals of the ligand to the 3s and 3p orbitals of the Na+ ion upon complexation.
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sodium thioether Macrocyclic Chemistry remarkable homoleptic octathia coordination to na
Inorganic Chemistry, 2015Co-Authors: Martin J. D. Champion, John M. Dyke, William Levason, Mark E. Light, David Pugh, Hanusha Bhakhoa, Lydia Rhyman, Ponnadurai Ramasami, Gillian ReidAbstract:Unprecedented homoleptic octathioether Macrocyclic coordination to Na+ in [Na([24]aneS8)]+ has been achieved by using Na[B{3,5-(CF3)2-C6H3}4] as a source of “naked” Na+ ions and confirmed crystallographically, with d(Na–S) = 2.9561(15)–3.0524(15) A. Density functional theory calculations show that there is electron transfer from the S 3p and C 2p valence orbitals of the ligand to the 3s and 3p orbitals of the Na+ ion upon complexation.
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selenoether Macrocyclic Chemistry syntheses and ligand properties of new small ring se3 and se2n donor macrocycles
Dalton Transactions, 2009Co-Authors: William Levason, Gillian Reid, Joanna M. Manning, Matthew Tuggey, Michael WebsterAbstract:Simultaneous dropwise addition of thf/EtOH solutions of Se{(CH2)3OTs}2 and o-C6H4(CH2SeCN)2 or NCSe(CH2)3SeCN to a suspension of NaBH4 in thf/EtOH at room temperature yields gram quantities of the 13- and 12-membered triselenoether macrocycles L1 and L2 respectively in high yield. The 11-membered ring L3 is obtained similarly by simultaneous dropwise addition of thf/EtOH solutions of Na2[o-C6H4Se2] (itself prepared by NaBH4reduction of the polymeric [o-C6H4Se2]n) and Se{(CH2)3OTs}2 to a suspension of NaBH4 in thf/EtOH. The small-ring, potentially tridentate Se2N(pyridyl)-donor macrocycles L4 and L5 were obtained in essentially quantitative yield by simultaneous dropwise addition of thf/EtOH solutions of 2,6-bis(bromomethyl)pyridine and either o-C6H4(CH2SeCN)2 or NCSe(CH2)3SeCN to a suspension of NaBH4 in thf/EtOH at room temperature. L1–L5 have been characterised by 1H, 13C{1H} and 77Se{1H} NMR spectroscopy, EI MS, and for L1 and L4, by X-ray crystal structures. Reaction of PtMe3I with one mol. equiv. of L (L = L1–L5) in refluxing CHCl3 gives the ionic complexes [PtMe3(L)]I cleanly and in good yield. These were characterised by 1H, 13C{1H}, 77Se{1H} and 195Pt NMR spectroscopy, electrospray MS, microanalyses and by crystal structures of [PtMe3(L1)]I and [PtMe3(L4)]I, which confirm distorted octahedral coordination at Pt(IV), with fac-tridentate coordination of the macrocycle in all cases, with anionic iodide. The complexes [PtCl2(L)] (L = L1–L3) were obtained as poorly soluble yellow-orange solids by reaction of PtCl2 with L in MeCN solution. The d3Cr(III) complexes of L (L = L1–L5) were obtained by reaction with [CrCl3(thf)3] in anhydrous CH2Cl2 as distorted octahedral fac-[CrCl3(L)], as poorly soluble blue-purple through to green powdered solids, which have been characterised by microanalysis, UV-visible and IR spectroscopy and by their magnetic moments. The properties of these complexes are compared with related chalcogenoether complexes from the literature involving thioether and acyclic selenoether coordination.
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Selenoether Macrocyclic Chemistry–syntheses and ligand properties of new small-ring Se3- and Se2N-donor macrocycles
Dalton transactions (Cambridge England : 2003), 2009Co-Authors: William Levason, Gillian Reid, Joanna M. Manning, Matthew Tuggey, Michael WebsterAbstract:Simultaneous dropwise addition of thf/EtOH solutions of Se{(CH2)3OTs}2 and o-C6H4(CH2SeCN)2 or NCSe(CH2)3SeCN to a suspension of NaBH4 in thf/EtOH at room temperature yields gram quantities of the 13- and 12-membered triselenoether macrocycles L1 and L2 respectively in high yield. The 11-membered ring L3 is obtained similarly by simultaneous dropwise addition of thf/EtOH solutions of Na2[o-C6H4Se2] (itself prepared by NaBH4reduction of the polymeric [o-C6H4Se2]n) and Se{(CH2)3OTs}2 to a suspension of NaBH4 in thf/EtOH. The small-ring, potentially tridentate Se2N(pyridyl)-donor macrocycles L4 and L5 were obtained in essentially quantitative yield by simultaneous dropwise addition of thf/EtOH solutions of 2,6-bis(bromomethyl)pyridine and either o-C6H4(CH2SeCN)2 or NCSe(CH2)3SeCN to a suspension of NaBH4 in thf/EtOH at room temperature. L1–L5 have been characterised by 1H, 13C{1H} and 77Se{1H} NMR spectroscopy, EI MS, and for L1 and L4, by X-ray crystal structures. Reaction of PtMe3I with one mol. equiv. of L (L = L1–L5) in refluxing CHCl3 gives the ionic complexes [PtMe3(L)]I cleanly and in good yield. These were characterised by 1H, 13C{1H}, 77Se{1H} and 195Pt NMR spectroscopy, electrospray MS, microanalyses and by crystal structures of [PtMe3(L1)]I and [PtMe3(L4)]I, which confirm distorted octahedral coordination at Pt(IV), with fac-tridentate coordination of the macrocycle in all cases, with anionic iodide. The complexes [PtCl2(L)] (L = L1–L3) were obtained as poorly soluble yellow-orange solids by reaction of PtCl2 with L in MeCN solution. The d3Cr(III) complexes of L (L = L1–L5) were obtained by reaction with [CrCl3(thf)3] in anhydrous CH2Cl2 as distorted octahedral fac-[CrCl3(L)], as poorly soluble blue-purple through to green powdered solids, which have been characterised by microanalysis, UV-visible and IR spectroscopy and by their magnetic moments. The properties of these complexes are compared with related chalcogenoether complexes from the literature involving thioether and acyclic selenoether coordination.
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selenoether Macrocyclic Chemistry syntheses and properties of new potentially tridentate and hexadentate se o donor macrocycles
Dalton Transactions, 2008Co-Authors: William Levason, Gillian Reid, Joanna M. Manning, Manisha Nirwan, Raju Ratnani, Hayley Smith, Michael WebsterAbstract: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 °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, 13C{1H} and 77Se{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.
Michael Webster - One of the best experts on this subject based on the ideXlab platform.
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selenoether Macrocyclic Chemistry syntheses and ligand properties of new small ring se3 and se2n donor macrocycles
Dalton Transactions, 2009Co-Authors: William Levason, Gillian Reid, Joanna M. Manning, Matthew Tuggey, Michael WebsterAbstract:Simultaneous dropwise addition of thf/EtOH solutions of Se{(CH2)3OTs}2 and o-C6H4(CH2SeCN)2 or NCSe(CH2)3SeCN to a suspension of NaBH4 in thf/EtOH at room temperature yields gram quantities of the 13- and 12-membered triselenoether macrocycles L1 and L2 respectively in high yield. The 11-membered ring L3 is obtained similarly by simultaneous dropwise addition of thf/EtOH solutions of Na2[o-C6H4Se2] (itself prepared by NaBH4reduction of the polymeric [o-C6H4Se2]n) and Se{(CH2)3OTs}2 to a suspension of NaBH4 in thf/EtOH. The small-ring, potentially tridentate Se2N(pyridyl)-donor macrocycles L4 and L5 were obtained in essentially quantitative yield by simultaneous dropwise addition of thf/EtOH solutions of 2,6-bis(bromomethyl)pyridine and either o-C6H4(CH2SeCN)2 or NCSe(CH2)3SeCN to a suspension of NaBH4 in thf/EtOH at room temperature. L1–L5 have been characterised by 1H, 13C{1H} and 77Se{1H} NMR spectroscopy, EI MS, and for L1 and L4, by X-ray crystal structures. Reaction of PtMe3I with one mol. equiv. of L (L = L1–L5) in refluxing CHCl3 gives the ionic complexes [PtMe3(L)]I cleanly and in good yield. These were characterised by 1H, 13C{1H}, 77Se{1H} and 195Pt NMR spectroscopy, electrospray MS, microanalyses and by crystal structures of [PtMe3(L1)]I and [PtMe3(L4)]I, which confirm distorted octahedral coordination at Pt(IV), with fac-tridentate coordination of the macrocycle in all cases, with anionic iodide. The complexes [PtCl2(L)] (L = L1–L3) were obtained as poorly soluble yellow-orange solids by reaction of PtCl2 with L in MeCN solution. The d3Cr(III) complexes of L (L = L1–L5) were obtained by reaction with [CrCl3(thf)3] in anhydrous CH2Cl2 as distorted octahedral fac-[CrCl3(L)], as poorly soluble blue-purple through to green powdered solids, which have been characterised by microanalysis, UV-visible and IR spectroscopy and by their magnetic moments. The properties of these complexes are compared with related chalcogenoether complexes from the literature involving thioether and acyclic selenoether coordination.
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Selenoether Macrocyclic Chemistry–syntheses and ligand properties of new small-ring Se3- and Se2N-donor macrocycles
Dalton transactions (Cambridge England : 2003), 2009Co-Authors: William Levason, Gillian Reid, Joanna M. Manning, Matthew Tuggey, Michael WebsterAbstract:Simultaneous dropwise addition of thf/EtOH solutions of Se{(CH2)3OTs}2 and o-C6H4(CH2SeCN)2 or NCSe(CH2)3SeCN to a suspension of NaBH4 in thf/EtOH at room temperature yields gram quantities of the 13- and 12-membered triselenoether macrocycles L1 and L2 respectively in high yield. The 11-membered ring L3 is obtained similarly by simultaneous dropwise addition of thf/EtOH solutions of Na2[o-C6H4Se2] (itself prepared by NaBH4reduction of the polymeric [o-C6H4Se2]n) and Se{(CH2)3OTs}2 to a suspension of NaBH4 in thf/EtOH. The small-ring, potentially tridentate Se2N(pyridyl)-donor macrocycles L4 and L5 were obtained in essentially quantitative yield by simultaneous dropwise addition of thf/EtOH solutions of 2,6-bis(bromomethyl)pyridine and either o-C6H4(CH2SeCN)2 or NCSe(CH2)3SeCN to a suspension of NaBH4 in thf/EtOH at room temperature. L1–L5 have been characterised by 1H, 13C{1H} and 77Se{1H} NMR spectroscopy, EI MS, and for L1 and L4, by X-ray crystal structures. Reaction of PtMe3I with one mol. equiv. of L (L = L1–L5) in refluxing CHCl3 gives the ionic complexes [PtMe3(L)]I cleanly and in good yield. These were characterised by 1H, 13C{1H}, 77Se{1H} and 195Pt NMR spectroscopy, electrospray MS, microanalyses and by crystal structures of [PtMe3(L1)]I and [PtMe3(L4)]I, which confirm distorted octahedral coordination at Pt(IV), with fac-tridentate coordination of the macrocycle in all cases, with anionic iodide. The complexes [PtCl2(L)] (L = L1–L3) were obtained as poorly soluble yellow-orange solids by reaction of PtCl2 with L in MeCN solution. The d3Cr(III) complexes of L (L = L1–L5) were obtained by reaction with [CrCl3(thf)3] in anhydrous CH2Cl2 as distorted octahedral fac-[CrCl3(L)], as poorly soluble blue-purple through to green powdered solids, which have been characterised by microanalysis, UV-visible and IR spectroscopy and by their magnetic moments. The properties of these complexes are compared with related chalcogenoether complexes from the literature involving thioether and acyclic selenoether coordination.
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selenoether Macrocyclic Chemistry syntheses and properties of new potentially tridentate and hexadentate se o donor macrocycles
Dalton Transactions, 2008Co-Authors: William Levason, Gillian Reid, Joanna M. Manning, Manisha Nirwan, Raju Ratnani, Hayley Smith, Michael WebsterAbstract: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 °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, 13C{1H} and 77Se{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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Selenoether Macrocyclic Chemistry—syntheses and properties of new potentially tridentate and hexadentate Se/O-donor macrocycles
Dalton transactions (Cambridge England : 2003), 2008Co-Authors: William Levason, Gillian Reid, Joanna M. Manning, Manisha Nirwan, Raju Ratnani, Hayley L. Smith, Michael WebsterAbstract: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 °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, 13C{1H} and 77Se{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.
Martin Schröder - One of the best experts on this subject based on the ideXlab platform.
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Platinum thioether Macrocyclic Chemistry: synthesis and electroChemistry of [PtL][PF6]2(L =[12]-, [14]- or [16]-aneS4) and [Pt2([28]aneS8)][PF6]4. Crystal structure of [Pt([12]aneS4)][PF6]2·MeCN
J. Chem. Soc. Dalton Trans., 1994Co-Authors: Alexander J. Blake, Gillian Reid, Alan J. Holder, Martin SchröderAbstract:A series of mono- and bi-nuclear platinum(II) complexes [PtL][PF6]2(L =[12]-, [14]- or [16]-aneS4) and [Pt2([28]aneS8)][PF6]4 have been synthesised by reaction of the crown thioethers with platinum(II) salts. Spectroscopic and structural data confirm square-planar homoleptic thioether co-ordination at PtII in each case. The complex [Pt([12]aneS4)][PF6]2·MeCN crystallises in the orthorhombic space group Pnma with a= 16.7983(9), b= 9.3213(7), c= 14.1954(8)A and Z= 4. The structure shows the cation disordered over a mirror plane, with the PtII ion bound to all four thioether donors in a distorted square-planar stereoChemistry, Pt–S(1) 2.266(4), Pt–S(4) 2.297(4)A, and the metal ion lying 0.282 A above the S4 co-ordination plane. The methylene carbons of the macrocycle are all directed to the opposite side of the S4 plane from the PtII ion leaving the top face of the metal centre exposed. Electrochemical studies on [PtL]2+ show an irreversible one-electron reduction at Epc=–1.41, –1.45 and –1.50 V vs. ferrocene–ferrocenium for L =[12]-, [14]- and [16]-aneS4 respectively at a scan rate of 180 mV s–1. The complex [Pt2([28]aneS8)]4+ exhibits an irreversible two-electron reduction at Epc=–1.48 V vs. ferrocene–ferrocenium.
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Organometallic Macrocyclic Chemistry: synthesis of cationic half-sandwich iridium(I) complexes of 1,4,7-trithiacyclononane ([9]aneS3). Crystal structures of [Ir([9]aneS3)(C2H4)2]PF6, [Ir([9]aneS3)(C8H12)]PF6 and [Ir([9]aneS3)(C4H6)]PF6·0.5Et2O
J. Chem. Soc. Dalton Trans., 1994Co-Authors: Alexander J. Blake, Malcolm A. Halcrow, Martin SchröderAbstract:Reaction of [Ir2L4Cl2](L = C8H14 or 0.5C8H12) or [IrL4Cl](L = C2H4 or 0.5C4H6) with 1 molar equivalent of 1,4,7-trithiacyclononane ([9]aneS3) and NH4PF6 in acetone, tetrahydrofuran or CH2Cl2 under N2 at 293 K afforded the complexes [Ir([9]aneS3)L2]PF6. The single-crystal structures of [Ir([9]aneS3)(C2H4)2]PF6 and [Ir([9]aneS3)(C8H12)]PF6 have been determined and show that the complex cations adopt distorted five-co-ordinate geometries. For [Ir([9]aneS3)(C2H4)2]PF6, Ir–S(1) 2.317(2), Ir–S(4) 2.402(2), Ir–S(7) 2.384(2), Ir–C(11) 2.173(9), Ir–C(12) 2.194(10), Ir–C(13) 2.146(8), Ir–C(14) 2.118(7), C(11)C(12) 1.366(13) and C(13)C(14) 1.443(11)A. For [Ir([9]aneS3)(C8H12)]PF6, Ir–S(1) 2.319(5), Ir–S(4) 2.343(4), Ir–S(7) 2.419(4), Ir–C(11) 2.166(14), Ir–C(12) 2.199(14), Ir–C(15) 2.188(15), Ir–C(16) 2.141(15), C(11)C(12) 1.411(19) and C(15)C(16) 1.418(21)A. The single-crystal structure of [Ir([9]aneS3)(C4H6)]PF6·0.5Et2O shows this complex to have a five-coordinate stereoChemistry analogous to that adopted by [Fe(CO)3(C4H6)] with Ir–S(1) 2.321(2), Ir–S(4) 2.331(2), Ir–S(7) 2.325(2), Ir–C(11) 2.149(9), Ir–C(12) 2.141(9), Ir–C(13) 2.146(9), Ir–C(14) 2.115(10), C(11)C(12) 1.433(13), C(12)–C(13) 1.381(13) and C(13)C(14) 1.461(14)A. Variable-temperature 1H and 13C NMR spectroscopic data on [M([9]aneS3)(C2H4)2]+ and [M([9]aneS3)(C4H6)]+(M = Rh or lr) are consistent with the highly electrophilic character of the cationic fragments [M([9]aneS3)]+. On the basis of J(C–H) coupling data and of an analysis of bond-length distributions and observed dihedral angles in the complex, the butadiene ligand in [Ir([9]aneS3)(C4H6)]+ is assigned as η4 bonded but with a significant σ2 component.
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Structural isomerism in silver thioether Macrocyclic Chemistry: the synthesis, redox properties and crystal structures of [Agn([15]aneS5)n][PF6]n′[Ag2([15]aneS5)2][BPh4]2 and [Ag([15]aneS5)][B(C6F5)4]([15]aneS5= 1,4,7,10,13-pentathiacyclopentadecane)
J. Chem. Soc. Dalton Trans., 1993Co-Authors: Alexander J. Blake, Gillian Reid, David Collison, Robert O. Gould, Martin SchröderAbstract:Reaction of AgNO3 with 1 molar equivalent of [15]aneS5(1,4,7,10,13-pentathiacyclopentadecane) in refluxing MeOH–water gives a colourless solution. Addition of excess of counter ion [PF6–, BPh4– or B(C6F5)4–] affords the colourless complexes [Agn([15]aneS5)n][PF6]n′[Ag2([15]aneS5)2][BPh4]2 and [Ag([15]aneS5)][B(C6F5)4] respectively in high yield. Single-crystal X-ray structural studies on these systems have revealed different cation stereochemistries as the counter ion is altered. Thus, [Agn([15]aneS5)n][PF6]n crystallises in the orthorhombic space group lba2 with a= 25.713(3), b= 25.749(3), c= 11.6989(19)A and Z= 16. The two independent infinite chains of cations in the structure are antiparallel. The stereoChemistry at Ag1 is severely distorted octahedral through an [S4+ S2] donor set, Ag(1)⋯ S(1) 3.219(5), Ag(1)–S(4) 2.659(5), Ag(1)–S(7) 2.651(6), Ag(1)⋯ S(10) 3.075(7), Ag(1)–S(13) 2.564(6)A, with one thioether donor from an adjacent [Ag([15]aneS5)]+ fragment asymmetrically bridging two metal centres, Ag(1)–S(1B) 2.742(5)A. A similar geometry is observed at the second Ag ion, Ag(2)⋯ S(1′) 3.263(5), Ag(2)–S(4′) 2.605(5), Ag(2)⋯ S(7′) 2.964(8), Ag(2)–S(10′) 2.713(7), Ag(2)–S(13′) 2.637(6), Ag(2)–S(1D) 2.714(5)A. The complex [Ag2([15]aneS5)2][BPh4]2 crystallises in the triclinic space group P with a= 11.462(3), b= 11.895(3), c= 27.019(10)A, α= 78.503(18), β= 84.729(13), γ= 67.118(18)°, and Z= 2. The structure of the [Ag2([15]aneS5)2]2+ cation shows an unusual binuclear stereoChemistry with [4 + 1] thioether donation to one silver(I) centre, Ag(2)–S(7′) 2.558(4), Ag(2)–S(10′) 2.623(5), Ag(2)–S(13′) 2.716(5), Ag(2)–S(1) 2.486(3), Ag(2)⋯ S(1′) 3.131(3)A, and [3 + 1] thioether donation to the other, Ag(1)–S(7) 2.529(3), Ag(1)–S(10) 2.608(4), Ag(1)–S(1′) 2.537(3), Ag(1)⋯ S(1) 2.907(3)A. Thus, one S-donor [S(1) and S(1′)] of each macrocycle bridges asymmetrically between the two metal centres. The complex [Ag([15]aneS5)][B(C6F5)4] crystallises in the triclinic space group P with a= 12.476(5), b= 13.658(7), c= 15.608(6)A, α= 108.300(22), β= 108.467(17), γ= 100.518(21)° and Z= 2. The structure contains discrete mononuclear [Ag([15]aneS5)]+ cations and [B(C6F5)4]– anions. The geometry at Ag1 is asymmetric with all five thioether donors of the macrocycle interacting with the metal centre: Ag–S(1) 2.4712(19), Ag ⋯ S(4) 2.7262(20), Ag–S(7) 2.6847(21), Ag–S(10) 2.5621(19), Ag ⋯ S(13) 2.8813(19)A. In MeCN solution [Ag([15]aneS5)]+ shows a chemically reversible AgI–AgII redox couple at E½= 0.76 V and a quasi-reversible AgI–Ago couple at –0.37 V vs. ferrocene–ferrocenium. The intensely coloured d9 silver(II) oxidation product has been observed by X- and Q-band ESR spectroscopy and the oxidation of AgI to AgII monitored spectroelectrochemically.
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Thallium Macrocyclic Chemistry: synthesis and crystal structures of [Tl([18]aneN2S4)]PF6 and [Tl([18]aneS6)]PF6([18]aneN2S4= 1,4,10,13-tetrathia-7,16-diazacyclooctadecane, [18]aneS6= 1,4,7,10,13,16-hexathiacyclooctadecane)
J. Chem. Soc. Dalton Trans., 1992Co-Authors: Alexander J. Blake, Gillian Reid, Martin SchröderAbstract:Reaction of TIPF6 with 1 molar equivalent of L (L =[18]aneN2S4 or [18]aneS6) in refluxing MeCN followed by addition of diethyl ether affords the 1 : 1 complex [TlL]PF6 in high yield. The complex [Tl([18]aneN2S4)]PF6 crystallises in the triclinic space group P with a= 9.733(6), b= 9.775(6), c= 11.370(8)A, α= 102.68(4), β= 92.35(4), γ= 95.05(5)° and Z= 2. The structure shows the thallium(I) ion occypying the ‘cardle’ formed by the macrocycle and bound via an [N2S2+ S2] donor set, Tl–S(4) 3.1299(13), Tl–S(13) 3.1445(13), Tl–N(7) 2.834(4), Tl–N(16) 2.992(4), Tl ⋯ S(1) 3.4778(15) and Tl ⋯ S(10) 3.4739(14)A. This leaves the top face of the metal centre exposed, except for long-range interactions with two further thioether donor atoms from adjacent [Tl([18]aneN2S4)]+ cations, Tl ⋯ S(1′) 3.643(1)(related by 1 –x, 1 –y, 1 –z), Tl ⋯ S(10″) 3.676(1)A(related by 1 –x, 1 –y, -z), and one F atom of the PF6– counter-ion, Tl ⋯ F(1) 3.326(4)A. The complex [Tl([18]aneS6)]PF6 crystallises in the monoclinic space group P21/c with a= 11.0279(13), b= 18.617(5), c= 10.8568(13)A, β= 96.876(13)° and Z= 4. The structure shows TlI interacting with all six Macrocyclic thioether donors; two of those interactions, Tl–S(1) 3.164(5) and Tl–S(13) 3.205(7)A, being considerably shorter than the other four, Tl ⋯ S(4) 3.370(5), Tl ⋯ S(7) 3.315(6), Tl ⋯ S(10) 3.347(7) and Tl ⋯ S(16) 3.356(6)A. There are additional long-range interactions with two further thioether donors from adjacent [Tl([18]aneS6)]+ cations, Tl ⋯ S(7prime;) 3.689(6)(related by –x, 1 –y, 1 –z) and Tl ⋯ S(16″) 3.688(6)A(related by 1 –x, 1 –y, 1 –z). There is also a long-range contact with one F atom of the PF6– counter-ion, Tl ⋯ F(6) 3.052(24)A.
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Thioether Macrocyclic Chemistry: Synthesis of [RhCl([15]aneS5)]2+ and [Ru(PPh3)([15]aneS5)]2+. The single crystal X-ray structure of [Ru(PPh3)([15]aneS5)](BPh4)2 ([15]aneS5 = 1,4,7,10,13-pentathiacyclopentadecane)
Polyhedron, 1992Co-Authors: Alexander J. Blake, G. Reid, Martin SchröderAbstract:Abstract Reaction of RhCl3 with one molar equivalent of [15]aneS5 in refluxing MeOH yields a yellow solution containing the complex cation [RhCl([15]aneS5)]2+. Addition of excess NH4PF6 affords the complex [RhCl([15]aneS5)](PF6)2 as a yellow solid, which can be recrystallized from MeCN. [RhCl([15]aneS5)]2+ shows two irreversible reductions at Epc = −0.78 and −1.93 V vs Fc/Fc+ at a scan rate of 200 mV s−1. Treatment of [RuCl2(PPh3)3] with one molar equivalent of [15]aneS5 in refluxing MeOH, followed by addition of excess NH4PF6 or NaBPh4 affords [Ru(PPh3)([15]aneS5)]X2 (X = PF6− or BPh4−) as a yellow solid, which can be recrystallized from MeCN/diethyl ether. [Ru(PPh3) ([15]aneS5)](BPh4)2 has been characterized by X-ray crystallography. The structure confirms coordination of all five Macrocyclic thioether donors, RuS(1) = 2.3371(15), RuS(4) = 2.3785(12), RuS(7) = 2.4458(10), RuS(10) = 2.3732(15), RuS(13) = 2.3099(10) A, and the P donor of the PPh3 ligand, RuP = 2.3679(8) A, to give an overall distorted octahedral stereoChemistry at ruthenium(II).
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Sodium thioether Macrocyclic Chemistry: remarkable homoleptic octathia coordination to Na+
Inorganic chemistry, 2015Co-Authors: Martin J. D. Champion, John M. Dyke, William Levason, Mark E. Light, David Pugh, Hanusha Bhakhoa, Lydia Rhyman, Ponnadurai Ramasami, Gillian ReidAbstract:Unprecedented homoleptic octathioether Macrocyclic coordination to Na+ in [Na([24]aneS8)]+ has been achieved by using Na[B{3,5-(CF3)2-C6H3}4] as a source of “naked” Na+ ions and confirmed crystallographically, with d(Na–S) = 2.9561(15)–3.0524(15) A. Density functional theory calculations show that there is electron transfer from the S 3p and C 2p valence orbitals of the ligand to the 3s and 3p orbitals of the Na+ ion upon complexation.
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sodium thioether Macrocyclic Chemistry remarkable homoleptic octathia coordination to na
Inorganic Chemistry, 2015Co-Authors: Martin J. D. Champion, John M. Dyke, William Levason, Mark E. Light, David Pugh, Hanusha Bhakhoa, Lydia Rhyman, Ponnadurai Ramasami, Gillian ReidAbstract:Unprecedented homoleptic octathioether Macrocyclic coordination to Na+ in [Na([24]aneS8)]+ has been achieved by using Na[B{3,5-(CF3)2-C6H3}4] as a source of “naked” Na+ ions and confirmed crystallographically, with d(Na–S) = 2.9561(15)–3.0524(15) A. Density functional theory calculations show that there is electron transfer from the S 3p and C 2p valence orbitals of the ligand to the 3s and 3p orbitals of the Na+ ion upon complexation.
