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Gerard Parkin - One of the best experts on this subject based on the ideXlab platform.
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organometallic zirconium compounds in an oxygen rich Coordination Environment synthesis and structural characterization of tris oxoimidazolyl hydroboratozirconium compounds
Inorganic Chemistry, 2018Co-Authors: Ahmed Alharbi, Matthew J Hammond, Gerard ParkinAbstract:A series of tris(oxoimidazolyl)hydroborato ligands, which serve as L2X [O3] donors, have been employed to obtain organometallic zirconium compounds in an uncommon oxygen-rich Coordination Environment. For example, Cp[ToMeBenz]ZrCl2 has been synthesized via the reaction of [ToMeBenz]Na with CpZrCl3 and bears a structural resemblance to the bent metallocene dichloride derivative Cp2ZrCl2. In addition, the half-sandwich counterparts [ToMeBenz]ZrCl3 and [ToBut]ZrCl3 have been obtained by metathesis of ZrCl4 with [ToMeBenz]Na and [ToBut]Na, respectively. The structurally related zirconium benzyl compounds [ToRBenz]Zr(CH2Ph)3 (R = Me, But, 1-Ad) have also been synthesized via the reactions of [ToRBenz]Tl with Zr(CH2Ph)4, and X-ray diffraction studies demonstrate that the benzyl ligands in these compounds are conformationally flexible and exhibit a large range of Zr–CH2–Ph bond angles (94.7–131.7°). Protolytic cleavage of one of the benzyl ligands of [ToRBenz]Zr(CH2Ph)3 (R = But, 1-Ad) may be achieved by treatme...
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Organometallic Zirconium Compounds in an Oxygen-Rich Coordination Environment: Synthesis and Structural Characterization of Tris(oxoimidazolyl)hydroboratozirconium Compounds
2018Co-Authors: Ahmed Al-harbi, Matthew J Hammond, Gerard ParkinAbstract:A series of tris(oxoimidazolyl)hydroborato ligands, which serve as L2X [O3] donors, have been employed to obtain organometallic zirconium compounds in an uncommon oxygen-rich Coordination Environment. For example, Cp[ToMeBenz]ZrCl2 has been synthesized via the reaction of [ToMeBenz]Na with CpZrCl3 and bears a structural resemblance to the bent metallocene dichloride derivative Cp2ZrCl2. In addition, the half-sandwich counterparts [ToMeBenz]ZrCl3 and [ToBut]ZrCl3 have been obtained by metathesis of ZrCl4 with [ToMeBenz]Na and [ToBut]Na, respectively. The structurally related zirconium benzyl compounds [ToRBenz]Zr(CH2Ph)3 (R = Me, But, 1-Ad) have also been synthesized via the reactions of [ToRBenz]Tl with Zr(CH2Ph)4, and X-ray diffraction studies demonstrate that the benzyl ligands in these compounds are conformationally flexible and exhibit a large range of Zr–CH2–Ph bond angles (94.7–131.7°). Protolytic cleavage of one of the benzyl ligands of [ToRBenz]Zr(CH2Ph)3 (R = But, 1-Ad) may be achieved by treatment with [PhNHMe2][B(C6F5)4] to generate {[ToRBenz]Zr(CH2Ph)2}[B(C6F5)4], which are catalysts for the polymerization of ethylene. The molecular structure of the ether adduct, {[ToButBenz]Zr(CH2Ph)2(OEt2)}[B(C6F5)4], has been determined by X-ray diffraction. In addition to the use of tris(oxoimidazolyl)hydroborato ligands, bis(oxoimidazolyl)hydroborato ligands have also been used to obtain zirconium benzyl compounds in oxygen-rich Environments, namely, [BoMeBenz]2Zr(CH2Ph)2 and [BoAdBenz]2Zr(CH2Ph)2
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Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [TmBut]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment.
Inorganic Chemistry, 2017Co-Authors: Ava Kreider-mueller, Jonathan S Owen, Patrick J Quinlivan, Gerard ParkinAbstract:A series of cadmium thiolate compounds that feature a sulfur-rich Coordination Environment, namely [TmBut]CdSAr, have been synthesized by the reactions of [TmBut]CdMe with ArSH (Ar = C6H4-4-F, C6H4-4-But, C6H4-4-OMe, and C6H4-3-OMe). In addition, the pyridine-2-thiolate and pyridine-2-selenolate derivatives, [TmBut]CdSPy and [TmBut]CdSePy have been obtained via the respective reactions of [TmBut]CdMe with pyridine-2-thione and pyridine-2-selone. The molecular structures of [TmBut]CdSAr and [TmBut]CdEPy (E = S or Se) have been determined by X-ray diffraction and demonstrate that, in each case, the [CdS4] motif is distorted tetrahedral and approaches a trigonal monopyramidal geometry in which the thiolate ligand adopts an equatorial position; [TmBut]CdSPy and [TmBut]CdSePy, however, exhibit an additional long-range interaction with the pyridyl nitrogen atoms. The ability of the thiolate ligands to participate in exchange was probed by 1H and 19F nuclear magnetic resonance (NMR) spectroscopic studies of the ...
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Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [TmBut]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment
2017Co-Authors: Ava Kreider-mueller, Jonathan S Owen, Patrick J Quinlivan, Gerard ParkinAbstract:A series of cadmium thiolate compounds that feature a sulfur-rich Coordination Environment, namely [TmBut]CdSAr, have been synthesized by the reactions of [TmBut]CdMe with ArSH (Ar = C6H4-4-F, C6H4-4-But, C6H4-4-OMe, and C6H4-3-OMe). In addition, the pyridine-2-thiolate and pyridine-2-selenolate derivatives, [TmBut]CdSPy and [TmBut]CdSePy have been obtained via the respective reactions of [TmBut]CdMe with pyridine-2-thione and pyridine-2-selone. The molecular structures of [TmBut]CdSAr and [TmBut]CdEPy (E = S or Se) have been determined by X-ray diffraction and demonstrate that, in each case, the [CdS4] motif is distorted tetrahedral and approaches a trigonal monopyramidal geometry in which the thiolate ligand adopts an equatorial position; [TmBut]CdSPy and [TmBut]CdSePy, however, exhibit an additional long-range interaction with the pyridyl nitrogen atoms. The ability of the thiolate ligands to participate in exchange was probed by 1H and 19F nuclear magnetic resonance (NMR) spectroscopic studies of the reactions of [TmBut]CdSC6H4-4-F with ArSH (Ar = C6H4-4-But or C6H4-4-OMe), which demonstrate that (i) exchange is facile and (ii) Coordination of thiolate to cadmium is most favored for the p-fluorophenyl derivative. Furthermore, a two-dimensional EXSY experiment involving [TmBut]CdSC6H4-4-F and 4-fluorothiophenol demonstrates that degenerate thiolate ligand exchange is also facile on the NMR time scale
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synthesis structure and reactivity of tmbut znh a monomeric terminal zinc hydride compound in a sulfur rich Coordination Environment access to a heterobimetallic compound
Chemical Communications, 2016Co-Authors: Ava Kreidermueller, Patrick J Quinlivan, Michael Rauch, Jonathan S Owen, Gerard ParkinAbstract:The first terminal zinc hydride complex that features a sulfur-rich Coordination Environment, namely the tris(2-mercapto-1-tert-butylimidazolyl)hydroborato compound, [TmBut]ZnH, has been synthesized via the reaction of [TmBut]ZnOPh with PhSiH3. The Zn–H bond of [TmBut]ZnH is subject to insertion of CO2 and facile protolytic cleavage, of which the latter provides access to heterobimetallic [TmBut]ZnMo(CO)3Cp.
Patrick J Quinlivan - One of the best experts on this subject based on the ideXlab platform.
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Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [TmBut]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment.
Inorganic Chemistry, 2017Co-Authors: Ava Kreider-mueller, Jonathan S Owen, Patrick J Quinlivan, Gerard ParkinAbstract:A series of cadmium thiolate compounds that feature a sulfur-rich Coordination Environment, namely [TmBut]CdSAr, have been synthesized by the reactions of [TmBut]CdMe with ArSH (Ar = C6H4-4-F, C6H4-4-But, C6H4-4-OMe, and C6H4-3-OMe). In addition, the pyridine-2-thiolate and pyridine-2-selenolate derivatives, [TmBut]CdSPy and [TmBut]CdSePy have been obtained via the respective reactions of [TmBut]CdMe with pyridine-2-thione and pyridine-2-selone. The molecular structures of [TmBut]CdSAr and [TmBut]CdEPy (E = S or Se) have been determined by X-ray diffraction and demonstrate that, in each case, the [CdS4] motif is distorted tetrahedral and approaches a trigonal monopyramidal geometry in which the thiolate ligand adopts an equatorial position; [TmBut]CdSPy and [TmBut]CdSePy, however, exhibit an additional long-range interaction with the pyridyl nitrogen atoms. The ability of the thiolate ligands to participate in exchange was probed by 1H and 19F nuclear magnetic resonance (NMR) spectroscopic studies of the ...
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Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [TmBut]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment
2017Co-Authors: Ava Kreider-mueller, Jonathan S Owen, Patrick J Quinlivan, Gerard ParkinAbstract:A series of cadmium thiolate compounds that feature a sulfur-rich Coordination Environment, namely [TmBut]CdSAr, have been synthesized by the reactions of [TmBut]CdMe with ArSH (Ar = C6H4-4-F, C6H4-4-But, C6H4-4-OMe, and C6H4-3-OMe). In addition, the pyridine-2-thiolate and pyridine-2-selenolate derivatives, [TmBut]CdSPy and [TmBut]CdSePy have been obtained via the respective reactions of [TmBut]CdMe with pyridine-2-thione and pyridine-2-selone. The molecular structures of [TmBut]CdSAr and [TmBut]CdEPy (E = S or Se) have been determined by X-ray diffraction and demonstrate that, in each case, the [CdS4] motif is distorted tetrahedral and approaches a trigonal monopyramidal geometry in which the thiolate ligand adopts an equatorial position; [TmBut]CdSPy and [TmBut]CdSePy, however, exhibit an additional long-range interaction with the pyridyl nitrogen atoms. The ability of the thiolate ligands to participate in exchange was probed by 1H and 19F nuclear magnetic resonance (NMR) spectroscopic studies of the reactions of [TmBut]CdSC6H4-4-F with ArSH (Ar = C6H4-4-But or C6H4-4-OMe), which demonstrate that (i) exchange is facile and (ii) Coordination of thiolate to cadmium is most favored for the p-fluorophenyl derivative. Furthermore, a two-dimensional EXSY experiment involving [TmBut]CdSC6H4-4-F and 4-fluorothiophenol demonstrates that degenerate thiolate ligand exchange is also facile on the NMR time scale
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synthesis structure and reactivity of tmbut znh a monomeric terminal zinc hydride compound in a sulfur rich Coordination Environment access to a heterobimetallic compound
Chemical Communications, 2016Co-Authors: Ava Kreidermueller, Patrick J Quinlivan, Michael Rauch, Jonathan S Owen, Gerard ParkinAbstract:The first terminal zinc hydride complex that features a sulfur-rich Coordination Environment, namely the tris(2-mercapto-1-tert-butylimidazolyl)hydroborato compound, [TmBut]ZnH, has been synthesized via the reaction of [TmBut]ZnOPh with PhSiH3. The Zn–H bond of [TmBut]ZnH is subject to insertion of CO2 and facile protolytic cleavage, of which the latter provides access to heterobimetallic [TmBut]ZnMo(CO)3Cp.
Jonathan S Owen - One of the best experts on this subject based on the ideXlab platform.
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Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [TmBut]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment.
Inorganic Chemistry, 2017Co-Authors: Ava Kreider-mueller, Jonathan S Owen, Patrick J Quinlivan, Gerard ParkinAbstract:A series of cadmium thiolate compounds that feature a sulfur-rich Coordination Environment, namely [TmBut]CdSAr, have been synthesized by the reactions of [TmBut]CdMe with ArSH (Ar = C6H4-4-F, C6H4-4-But, C6H4-4-OMe, and C6H4-3-OMe). In addition, the pyridine-2-thiolate and pyridine-2-selenolate derivatives, [TmBut]CdSPy and [TmBut]CdSePy have been obtained via the respective reactions of [TmBut]CdMe with pyridine-2-thione and pyridine-2-selone. The molecular structures of [TmBut]CdSAr and [TmBut]CdEPy (E = S or Se) have been determined by X-ray diffraction and demonstrate that, in each case, the [CdS4] motif is distorted tetrahedral and approaches a trigonal monopyramidal geometry in which the thiolate ligand adopts an equatorial position; [TmBut]CdSPy and [TmBut]CdSePy, however, exhibit an additional long-range interaction with the pyridyl nitrogen atoms. The ability of the thiolate ligands to participate in exchange was probed by 1H and 19F nuclear magnetic resonance (NMR) spectroscopic studies of the ...
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Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [TmBut]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment
2017Co-Authors: Ava Kreider-mueller, Jonathan S Owen, Patrick J Quinlivan, Gerard ParkinAbstract:A series of cadmium thiolate compounds that feature a sulfur-rich Coordination Environment, namely [TmBut]CdSAr, have been synthesized by the reactions of [TmBut]CdMe with ArSH (Ar = C6H4-4-F, C6H4-4-But, C6H4-4-OMe, and C6H4-3-OMe). In addition, the pyridine-2-thiolate and pyridine-2-selenolate derivatives, [TmBut]CdSPy and [TmBut]CdSePy have been obtained via the respective reactions of [TmBut]CdMe with pyridine-2-thione and pyridine-2-selone. The molecular structures of [TmBut]CdSAr and [TmBut]CdEPy (E = S or Se) have been determined by X-ray diffraction and demonstrate that, in each case, the [CdS4] motif is distorted tetrahedral and approaches a trigonal monopyramidal geometry in which the thiolate ligand adopts an equatorial position; [TmBut]CdSPy and [TmBut]CdSePy, however, exhibit an additional long-range interaction with the pyridyl nitrogen atoms. The ability of the thiolate ligands to participate in exchange was probed by 1H and 19F nuclear magnetic resonance (NMR) spectroscopic studies of the reactions of [TmBut]CdSC6H4-4-F with ArSH (Ar = C6H4-4-But or C6H4-4-OMe), which demonstrate that (i) exchange is facile and (ii) Coordination of thiolate to cadmium is most favored for the p-fluorophenyl derivative. Furthermore, a two-dimensional EXSY experiment involving [TmBut]CdSC6H4-4-F and 4-fluorothiophenol demonstrates that degenerate thiolate ligand exchange is also facile on the NMR time scale
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synthesis structure and reactivity of tmbut znh a monomeric terminal zinc hydride compound in a sulfur rich Coordination Environment access to a heterobimetallic compound
Chemical Communications, 2016Co-Authors: Ava Kreidermueller, Patrick J Quinlivan, Michael Rauch, Jonathan S Owen, Gerard ParkinAbstract:The first terminal zinc hydride complex that features a sulfur-rich Coordination Environment, namely the tris(2-mercapto-1-tert-butylimidazolyl)hydroborato compound, [TmBut]ZnH, has been synthesized via the reaction of [TmBut]ZnOPh with PhSiH3. The Zn–H bond of [TmBut]ZnH is subject to insertion of CO2 and facile protolytic cleavage, of which the latter provides access to heterobimetallic [TmBut]ZnMo(CO)3Cp.
Yuichi Shimakawa - One of the best experts on this subject based on the ideXlab platform.
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tuning magnetic anisotropy by interfacially engineering the oxygen Coordination Environment in a transition metal oxide
Nature Materials, 2016Co-Authors: Riko Sato, Mitsutaka Haruta, Hiroki Kurata, Yuichi ShimakawaAbstract:The thickness of Ca0.5Sr0.5TiO3 is found to modify the oxygen Coordination Environment of SrRuO3 in the heterostructure GdScO3/Ca0.5Sr0.5TiO3/SrRuO3, also allowing the magnetic anisotropy to be tuned in the entire SrRuO3 layer.
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Tuning magnetic anisotropy by interfacially engineering the oxygen Coordination Environment in a transition metal oxide
Nature materials, 2016Co-Authors: Daisuke Kan, Riko Sato, Mitsutaka Haruta, Hiroki Kurata, Ryotaro Aso, Yuichi ShimakawaAbstract:Strong correlations between electrons, spins and lattices--stemming from strong hybridization between transition metal d and oxygen p orbitals--are responsible for the functional properties of transition metal oxides. Artificial oxide heterostructures with chemically abrupt interfaces provide a platform for engineering bonding geometries that lead to emergent phenomena. Here we demonstrate the control of the oxygen Coordination Environment of the perovskite, SrRuO3, by heterostructuring it with Ca0.5Sr0.5TiO3 (0-4 monolayers thick) grown on a GdScO3 substrate. We found that a Ru-O-Ti bond angle of the SrRuO3 /Ca0.5Sr0.5TiO3 interface can be engineered by layer-by-layer control of the Ca0.5Sr0.5TiO3 layer thickness, and that the engineered Ru-O-Ti bond angle not only stabilizes a Ru-O-Ru bond angle never seen in bulk SrRuO3, but also tunes the magnetic anisotropy in the entire SrRuO3 layer. The results demonstrate that interface engineering of the oxygen Coordination Environment allows one to control additional degrees of freedom in functional oxide heterostructures.
Ava Kreider-mueller - One of the best experts on this subject based on the ideXlab platform.
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Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [TmBut]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment.
Inorganic Chemistry, 2017Co-Authors: Ava Kreider-mueller, Jonathan S Owen, Patrick J Quinlivan, Gerard ParkinAbstract:A series of cadmium thiolate compounds that feature a sulfur-rich Coordination Environment, namely [TmBut]CdSAr, have been synthesized by the reactions of [TmBut]CdMe with ArSH (Ar = C6H4-4-F, C6H4-4-But, C6H4-4-OMe, and C6H4-3-OMe). In addition, the pyridine-2-thiolate and pyridine-2-selenolate derivatives, [TmBut]CdSPy and [TmBut]CdSePy have been obtained via the respective reactions of [TmBut]CdMe with pyridine-2-thione and pyridine-2-selone. The molecular structures of [TmBut]CdSAr and [TmBut]CdEPy (E = S or Se) have been determined by X-ray diffraction and demonstrate that, in each case, the [CdS4] motif is distorted tetrahedral and approaches a trigonal monopyramidal geometry in which the thiolate ligand adopts an equatorial position; [TmBut]CdSPy and [TmBut]CdSePy, however, exhibit an additional long-range interaction with the pyridyl nitrogen atoms. The ability of the thiolate ligands to participate in exchange was probed by 1H and 19F nuclear magnetic resonance (NMR) spectroscopic studies of the ...
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Tris(2-mercaptoimidazolyl)hydroborato Cadmium Thiolate Complexes, [TmBut]CdSAr: Thiolate Exchange at Cadmium in a Sulfur-Rich Coordination Environment
2017Co-Authors: Ava Kreider-mueller, Jonathan S Owen, Patrick J Quinlivan, Gerard ParkinAbstract:A series of cadmium thiolate compounds that feature a sulfur-rich Coordination Environment, namely [TmBut]CdSAr, have been synthesized by the reactions of [TmBut]CdMe with ArSH (Ar = C6H4-4-F, C6H4-4-But, C6H4-4-OMe, and C6H4-3-OMe). In addition, the pyridine-2-thiolate and pyridine-2-selenolate derivatives, [TmBut]CdSPy and [TmBut]CdSePy have been obtained via the respective reactions of [TmBut]CdMe with pyridine-2-thione and pyridine-2-selone. The molecular structures of [TmBut]CdSAr and [TmBut]CdEPy (E = S or Se) have been determined by X-ray diffraction and demonstrate that, in each case, the [CdS4] motif is distorted tetrahedral and approaches a trigonal monopyramidal geometry in which the thiolate ligand adopts an equatorial position; [TmBut]CdSPy and [TmBut]CdSePy, however, exhibit an additional long-range interaction with the pyridyl nitrogen atoms. The ability of the thiolate ligands to participate in exchange was probed by 1H and 19F nuclear magnetic resonance (NMR) spectroscopic studies of the reactions of [TmBut]CdSC6H4-4-F with ArSH (Ar = C6H4-4-But or C6H4-4-OMe), which demonstrate that (i) exchange is facile and (ii) Coordination of thiolate to cadmium is most favored for the p-fluorophenyl derivative. Furthermore, a two-dimensional EXSY experiment involving [TmBut]CdSC6H4-4-F and 4-fluorothiophenol demonstrates that degenerate thiolate ligand exchange is also facile on the NMR time scale