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Ignacio Vargas-baca - One of the best experts on this subject based on the ideXlab platform.
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CH–NH Tautomerism in the Products of the Reactions of the Methanide [HC(PPh2NSiMe3)2]− with Pnictogen and Tellurium Iodides
Organometallics, 2013Co-Authors: Ramalingam Thirumoorthi, Tristram Chivers, Chris Gendy, Ignacio Vargas-bacaAbstract:The reactions of K[HC(PPh2NSiMe3)2] (K[1]) and MI3 (M = As, Sb) or TeI4 gave as the major products the complexes [{MIn}{C(PPh2NSiMe3)(PPh2NHSiMe3)}] (MIn = trans-AsI2, trans- or cis-SbI2, TeI3), which feature the ligand [C(PPh2NSiMe3)(PPh2NHSiMe3)]− (2). This anion, the NH tautomer of [HC(PPh2NSiMe3)2]−, is formally generated by a 1,3-hydrogen shift to give complexes in which the ligand is N,C-chelated to the main-group-metalloid center. The M–C distances are slightly longer than the sum of the covalent radii for M and C in the case of the group 15 metalloids but significantly shorter for M = Te. The arsenic Derivative [{t-AsI2}2] is monomeric in the solid state, with As–I distances that differ by ca. 0.55 A, whereas the antimony analogues [{t-SbI2}2] and [{c-SbI2}2] are dimeric through bridging iodide ligands and the disparity in Sb–I distances of the SbI2 units is 0.10 and 0.33 A, respectively. The Tellurium Derivative [{TeI3}2] is monomeric with a distorted-square-pyramidal geometry at the Te center an...
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CH–NH Tautomerism in the Products of the Reactions of the Methanide [HC(PPh2NSiMe3)2]− with Pnictogen and Tellurium Iodides
2013Co-Authors: Ramalingam Thirumoorthi, Tristram Chivers, Chris Gendy, Ignacio Vargas-bacaAbstract:The reactions of K[HC(PPh2NSiMe3)2] (K[1]) and MI3 (M = As, Sb) or TeI4 gave as the major products the complexes [{MIn}{C(PPh2NSiMe3)(PPh2NHSiMe3)}] (MIn = trans-AsI2, trans- or cis-SbI2, TeI3), which feature the ligand [C(PPh2NSiMe3)(PPh2NHSiMe3)]− (2). This anion, the NH tautomer of [HC(PPh2NSiMe3)2]−, is formally generated by a 1,3-hydrogen shift to give complexes in which the ligand is N,C-chelated to the main-group-metalloid center. The M–C distances are slightly longer than the sum of the covalent radii for M and C in the case of the group 15 metalloids but significantly shorter for M = Te. The arsenic Derivative [{t-AsI2}2] is monomeric in the solid state, with As–I distances that differ by ca. 0.55 Å, whereas the antimony analogues [{t-SbI2}2] and [{c-SbI2}2] are dimeric through bridging iodide ligands and the disparity in Sb–I distances of the SbI2 units is 0.10 and 0.33 Å, respectively. The Tellurium Derivative [{TeI3}2] is monomeric with a distorted-square-pyramidal geometry at the Te center and Te–I distances in the narrow range 2.9142(4)–3.0337(4) Å. In contrast to the lighter pnictogens, the bismuth complex [{t-BiI2}1] is comprised of the methanide 1 coordinated in a tridentate (N,C,N) mode to a BiI2+ cation. In the case of arsenic triiodide, the metathesis is accompanied by Si–N bond cleavage to give [{AsI2}{CH2(PPh2N)(PPh2NSiMe3)}] (3), which was characterized by 31P NMR spectroscopy, and conversion to the corresponding salt [{AsI}{CH2(PPh2N)(PPh2NSiMe3)}][SbF6] (3A) by treatment with AgSbF6. The As–N distances in the six-membered CP2N2As ring in 3A differ by 0.20 Å due to the different coordination numbers (2 and 3) of the two N atoms in the novel N,N′-chelated [CH2(PPh2N)(PPh2NSiMe3)]− anion. In contrast, reaction of [{t-SbI2}2] with AgSbF6 gives the expected salt as the dimer {[{SbI}2][SbF6]}2. The two hydrolysis products [CH2(PPh2NSiMe3)(PPh2NHSiMe3)][SbF6] (4A) and [CH2(PPh2NSiMe3) (PPh2NHSiMe3)]2[Te2I6] (4B) were also structurally characterized and shown to contain the same cation. DFT calculations indicate that the N–H tautomer 2 is stabilized by strong M–N and M–C bonding interactions which include a small degree of π character. Weaker bonds, as in the Bi complex, favor the C–H tautomer 1 as the ligand
Ramalingam Thirumoorthi - One of the best experts on this subject based on the ideXlab platform.
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CH–NH Tautomerism in the Products of the Reactions of the Methanide [HC(PPh2NSiMe3)2]− with Pnictogen and Tellurium Iodides
Organometallics, 2013Co-Authors: Ramalingam Thirumoorthi, Tristram Chivers, Chris Gendy, Ignacio Vargas-bacaAbstract:The reactions of K[HC(PPh2NSiMe3)2] (K[1]) and MI3 (M = As, Sb) or TeI4 gave as the major products the complexes [{MIn}{C(PPh2NSiMe3)(PPh2NHSiMe3)}] (MIn = trans-AsI2, trans- or cis-SbI2, TeI3), which feature the ligand [C(PPh2NSiMe3)(PPh2NHSiMe3)]− (2). This anion, the NH tautomer of [HC(PPh2NSiMe3)2]−, is formally generated by a 1,3-hydrogen shift to give complexes in which the ligand is N,C-chelated to the main-group-metalloid center. The M–C distances are slightly longer than the sum of the covalent radii for M and C in the case of the group 15 metalloids but significantly shorter for M = Te. The arsenic Derivative [{t-AsI2}2] is monomeric in the solid state, with As–I distances that differ by ca. 0.55 A, whereas the antimony analogues [{t-SbI2}2] and [{c-SbI2}2] are dimeric through bridging iodide ligands and the disparity in Sb–I distances of the SbI2 units is 0.10 and 0.33 A, respectively. The Tellurium Derivative [{TeI3}2] is monomeric with a distorted-square-pyramidal geometry at the Te center an...
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CH–NH Tautomerism in the Products of the Reactions of the Methanide [HC(PPh2NSiMe3)2]− with Pnictogen and Tellurium Iodides
2013Co-Authors: Ramalingam Thirumoorthi, Tristram Chivers, Chris Gendy, Ignacio Vargas-bacaAbstract:The reactions of K[HC(PPh2NSiMe3)2] (K[1]) and MI3 (M = As, Sb) or TeI4 gave as the major products the complexes [{MIn}{C(PPh2NSiMe3)(PPh2NHSiMe3)}] (MIn = trans-AsI2, trans- or cis-SbI2, TeI3), which feature the ligand [C(PPh2NSiMe3)(PPh2NHSiMe3)]− (2). This anion, the NH tautomer of [HC(PPh2NSiMe3)2]−, is formally generated by a 1,3-hydrogen shift to give complexes in which the ligand is N,C-chelated to the main-group-metalloid center. The M–C distances are slightly longer than the sum of the covalent radii for M and C in the case of the group 15 metalloids but significantly shorter for M = Te. The arsenic Derivative [{t-AsI2}2] is monomeric in the solid state, with As–I distances that differ by ca. 0.55 Å, whereas the antimony analogues [{t-SbI2}2] and [{c-SbI2}2] are dimeric through bridging iodide ligands and the disparity in Sb–I distances of the SbI2 units is 0.10 and 0.33 Å, respectively. The Tellurium Derivative [{TeI3}2] is monomeric with a distorted-square-pyramidal geometry at the Te center and Te–I distances in the narrow range 2.9142(4)–3.0337(4) Å. In contrast to the lighter pnictogens, the bismuth complex [{t-BiI2}1] is comprised of the methanide 1 coordinated in a tridentate (N,C,N) mode to a BiI2+ cation. In the case of arsenic triiodide, the metathesis is accompanied by Si–N bond cleavage to give [{AsI2}{CH2(PPh2N)(PPh2NSiMe3)}] (3), which was characterized by 31P NMR spectroscopy, and conversion to the corresponding salt [{AsI}{CH2(PPh2N)(PPh2NSiMe3)}][SbF6] (3A) by treatment with AgSbF6. The As–N distances in the six-membered CP2N2As ring in 3A differ by 0.20 Å due to the different coordination numbers (2 and 3) of the two N atoms in the novel N,N′-chelated [CH2(PPh2N)(PPh2NSiMe3)]− anion. In contrast, reaction of [{t-SbI2}2] with AgSbF6 gives the expected salt as the dimer {[{SbI}2][SbF6]}2. The two hydrolysis products [CH2(PPh2NSiMe3)(PPh2NHSiMe3)][SbF6] (4A) and [CH2(PPh2NSiMe3) (PPh2NHSiMe3)]2[Te2I6] (4B) were also structurally characterized and shown to contain the same cation. DFT calculations indicate that the N–H tautomer 2 is stabilized by strong M–N and M–C bonding interactions which include a small degree of π character. Weaker bonds, as in the Bi complex, favor the C–H tautomer 1 as the ligand
Tristram Chivers - One of the best experts on this subject based on the ideXlab platform.
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CH–NH Tautomerism in the Products of the Reactions of the Methanide [HC(PPh2NSiMe3)2]− with Pnictogen and Tellurium Iodides
Organometallics, 2013Co-Authors: Ramalingam Thirumoorthi, Tristram Chivers, Chris Gendy, Ignacio Vargas-bacaAbstract:The reactions of K[HC(PPh2NSiMe3)2] (K[1]) and MI3 (M = As, Sb) or TeI4 gave as the major products the complexes [{MIn}{C(PPh2NSiMe3)(PPh2NHSiMe3)}] (MIn = trans-AsI2, trans- or cis-SbI2, TeI3), which feature the ligand [C(PPh2NSiMe3)(PPh2NHSiMe3)]− (2). This anion, the NH tautomer of [HC(PPh2NSiMe3)2]−, is formally generated by a 1,3-hydrogen shift to give complexes in which the ligand is N,C-chelated to the main-group-metalloid center. The M–C distances are slightly longer than the sum of the covalent radii for M and C in the case of the group 15 metalloids but significantly shorter for M = Te. The arsenic Derivative [{t-AsI2}2] is monomeric in the solid state, with As–I distances that differ by ca. 0.55 A, whereas the antimony analogues [{t-SbI2}2] and [{c-SbI2}2] are dimeric through bridging iodide ligands and the disparity in Sb–I distances of the SbI2 units is 0.10 and 0.33 A, respectively. The Tellurium Derivative [{TeI3}2] is monomeric with a distorted-square-pyramidal geometry at the Te center an...
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CH–NH Tautomerism in the Products of the Reactions of the Methanide [HC(PPh2NSiMe3)2]− with Pnictogen and Tellurium Iodides
2013Co-Authors: Ramalingam Thirumoorthi, Tristram Chivers, Chris Gendy, Ignacio Vargas-bacaAbstract:The reactions of K[HC(PPh2NSiMe3)2] (K[1]) and MI3 (M = As, Sb) or TeI4 gave as the major products the complexes [{MIn}{C(PPh2NSiMe3)(PPh2NHSiMe3)}] (MIn = trans-AsI2, trans- or cis-SbI2, TeI3), which feature the ligand [C(PPh2NSiMe3)(PPh2NHSiMe3)]− (2). This anion, the NH tautomer of [HC(PPh2NSiMe3)2]−, is formally generated by a 1,3-hydrogen shift to give complexes in which the ligand is N,C-chelated to the main-group-metalloid center. The M–C distances are slightly longer than the sum of the covalent radii for M and C in the case of the group 15 metalloids but significantly shorter for M = Te. The arsenic Derivative [{t-AsI2}2] is monomeric in the solid state, with As–I distances that differ by ca. 0.55 Å, whereas the antimony analogues [{t-SbI2}2] and [{c-SbI2}2] are dimeric through bridging iodide ligands and the disparity in Sb–I distances of the SbI2 units is 0.10 and 0.33 Å, respectively. The Tellurium Derivative [{TeI3}2] is monomeric with a distorted-square-pyramidal geometry at the Te center and Te–I distances in the narrow range 2.9142(4)–3.0337(4) Å. In contrast to the lighter pnictogens, the bismuth complex [{t-BiI2}1] is comprised of the methanide 1 coordinated in a tridentate (N,C,N) mode to a BiI2+ cation. In the case of arsenic triiodide, the metathesis is accompanied by Si–N bond cleavage to give [{AsI2}{CH2(PPh2N)(PPh2NSiMe3)}] (3), which was characterized by 31P NMR spectroscopy, and conversion to the corresponding salt [{AsI}{CH2(PPh2N)(PPh2NSiMe3)}][SbF6] (3A) by treatment with AgSbF6. The As–N distances in the six-membered CP2N2As ring in 3A differ by 0.20 Å due to the different coordination numbers (2 and 3) of the two N atoms in the novel N,N′-chelated [CH2(PPh2N)(PPh2NSiMe3)]− anion. In contrast, reaction of [{t-SbI2}2] with AgSbF6 gives the expected salt as the dimer {[{SbI}2][SbF6]}2. The two hydrolysis products [CH2(PPh2NSiMe3)(PPh2NHSiMe3)][SbF6] (4A) and [CH2(PPh2NSiMe3) (PPh2NHSiMe3)]2[Te2I6] (4B) were also structurally characterized and shown to contain the same cation. DFT calculations indicate that the N–H tautomer 2 is stabilized by strong M–N and M–C bonding interactions which include a small degree of π character. Weaker bonds, as in the Bi complex, favor the C–H tautomer 1 as the ligand
Chris Gendy - One of the best experts on this subject based on the ideXlab platform.
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CH–NH Tautomerism in the Products of the Reactions of the Methanide [HC(PPh2NSiMe3)2]− with Pnictogen and Tellurium Iodides
Organometallics, 2013Co-Authors: Ramalingam Thirumoorthi, Tristram Chivers, Chris Gendy, Ignacio Vargas-bacaAbstract:The reactions of K[HC(PPh2NSiMe3)2] (K[1]) and MI3 (M = As, Sb) or TeI4 gave as the major products the complexes [{MIn}{C(PPh2NSiMe3)(PPh2NHSiMe3)}] (MIn = trans-AsI2, trans- or cis-SbI2, TeI3), which feature the ligand [C(PPh2NSiMe3)(PPh2NHSiMe3)]− (2). This anion, the NH tautomer of [HC(PPh2NSiMe3)2]−, is formally generated by a 1,3-hydrogen shift to give complexes in which the ligand is N,C-chelated to the main-group-metalloid center. The M–C distances are slightly longer than the sum of the covalent radii for M and C in the case of the group 15 metalloids but significantly shorter for M = Te. The arsenic Derivative [{t-AsI2}2] is monomeric in the solid state, with As–I distances that differ by ca. 0.55 A, whereas the antimony analogues [{t-SbI2}2] and [{c-SbI2}2] are dimeric through bridging iodide ligands and the disparity in Sb–I distances of the SbI2 units is 0.10 and 0.33 A, respectively. The Tellurium Derivative [{TeI3}2] is monomeric with a distorted-square-pyramidal geometry at the Te center an...
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CH–NH Tautomerism in the Products of the Reactions of the Methanide [HC(PPh2NSiMe3)2]− with Pnictogen and Tellurium Iodides
2013Co-Authors: Ramalingam Thirumoorthi, Tristram Chivers, Chris Gendy, Ignacio Vargas-bacaAbstract:The reactions of K[HC(PPh2NSiMe3)2] (K[1]) and MI3 (M = As, Sb) or TeI4 gave as the major products the complexes [{MIn}{C(PPh2NSiMe3)(PPh2NHSiMe3)}] (MIn = trans-AsI2, trans- or cis-SbI2, TeI3), which feature the ligand [C(PPh2NSiMe3)(PPh2NHSiMe3)]− (2). This anion, the NH tautomer of [HC(PPh2NSiMe3)2]−, is formally generated by a 1,3-hydrogen shift to give complexes in which the ligand is N,C-chelated to the main-group-metalloid center. The M–C distances are slightly longer than the sum of the covalent radii for M and C in the case of the group 15 metalloids but significantly shorter for M = Te. The arsenic Derivative [{t-AsI2}2] is monomeric in the solid state, with As–I distances that differ by ca. 0.55 Å, whereas the antimony analogues [{t-SbI2}2] and [{c-SbI2}2] are dimeric through bridging iodide ligands and the disparity in Sb–I distances of the SbI2 units is 0.10 and 0.33 Å, respectively. The Tellurium Derivative [{TeI3}2] is monomeric with a distorted-square-pyramidal geometry at the Te center and Te–I distances in the narrow range 2.9142(4)–3.0337(4) Å. In contrast to the lighter pnictogens, the bismuth complex [{t-BiI2}1] is comprised of the methanide 1 coordinated in a tridentate (N,C,N) mode to a BiI2+ cation. In the case of arsenic triiodide, the metathesis is accompanied by Si–N bond cleavage to give [{AsI2}{CH2(PPh2N)(PPh2NSiMe3)}] (3), which was characterized by 31P NMR spectroscopy, and conversion to the corresponding salt [{AsI}{CH2(PPh2N)(PPh2NSiMe3)}][SbF6] (3A) by treatment with AgSbF6. The As–N distances in the six-membered CP2N2As ring in 3A differ by 0.20 Å due to the different coordination numbers (2 and 3) of the two N atoms in the novel N,N′-chelated [CH2(PPh2N)(PPh2NSiMe3)]− anion. In contrast, reaction of [{t-SbI2}2] with AgSbF6 gives the expected salt as the dimer {[{SbI}2][SbF6]}2. The two hydrolysis products [CH2(PPh2NSiMe3)(PPh2NHSiMe3)][SbF6] (4A) and [CH2(PPh2NSiMe3) (PPh2NHSiMe3)]2[Te2I6] (4B) were also structurally characterized and shown to contain the same cation. DFT calculations indicate that the N–H tautomer 2 is stabilized by strong M–N and M–C bonding interactions which include a small degree of π character. Weaker bonds, as in the Bi complex, favor the C–H tautomer 1 as the ligand
Sato, Roseli Hiromi - One of the best experts on this subject based on the ideXlab platform.
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Desenvolvimento de metodologia para modificação química reversível de superfícies de microcantilevers com aplicação em biossensores nanomecânicos
2015Co-Authors: Sato, Roseli HiromiAbstract:Orientador: Prof. Dr. Pablo Alejandro FioritoDissertação (mestrado) - Universidade Federal do ABC. Programa de Pós-Graduação em Ciência e Tecnologia/Química, 2015.Nos últimos anos, houve uma grande expansão na busca e desenvolvimento de novos dispositivos voltados para a área de biossensores. Tendo em vista esta grande demanda relacionada ao desenvolvimento de novos dispositivos para detecção de determinadas biomoléculas, como ácidos desoxirribonucleicos (DNA), este trabalho descreve o desenvolvimento de um método para modificação química reversível de superfícies de microcantilevers que são aplicados em estudos de biossensores nanomecânicos. Dessa maneira, para a elaboração desta metodologia foi utilizado o conceito de Click Chemistry aliado à atividade redox de compostos de telúrio junto a grupos tióis, grupo este, que está presente em muitas biomoléculas aplicadas em processos de detecção em biossensores. A parte inicial deste trabalho consistiu na síntese de teluretos bis-arílicos não simétricos, no qual foi possível obter um rendimento isolado para o telureto de 3-nitrofenil 4-metoxifenila de 90%. Após a obtenção deste composto, foram realizadas mais duas etapas de síntese para obtenção do ácido 4-((3-((4-metoxifenil)teluro)fenil)amino)-4-oxobutanóico sendo obtido um rendimento isolado de 60%. Este derivado de telúrio foi imobilizado sobre a superfície de microcantilevers sendo possível verificar a sua atividade redox junto à biomoléculas tioladas de DNA. Paralelamente foi realizado um estudo de viabilidade para troca de biomoléculas que atuam como "receptores" no processo de detecção da fita complementária de DNA. Este resultado se torna relevante, pois possibilita realizar a troca do sistema de detecção a partir da regeneração da superfície além de demonstrar a eficácia da proposta deste trabalho.In recent years, it has been a great expansion in the search and development of new devices focused on biosensors area. In view of this high demand related to the development of new devices for the detection of certain biomolecules, like deoxyribonucleic acid (DNA) ones, this work describes the development of method for reversible chemical modification of surfaces of microcantilevers are used in biosensors nanomechanical studies. Thus, for the preparation of this methodology it was used the concept of Click Chemistry together with the redox activity of Tellurium compounds with thiol groups, which is present in many biomolecules applied to detection processes in biosensors. The initial part of this work involved the synthesis of unsymmetrical diaryl tellurides, in which it was possible to obtain an isolated yield for the telluride of 3-nitrophenyl 4- (4-methoxyphenyl)(3-nitrophenyl)tellane of 90%. After obtaining this compound two more synthesis steps for obtaining acid 4 - ((3 - ((4-methoxyphenyl) teluro) phenyl) amino) -4-oxobutanoic acid were performed being obtained an isolated yield of 60%. The Tellurium Derivative was immobilized on the surface of microcantilevers being possible to verify its redox activity by biomolecules (DNA) with thiol groups. At the same time it carried out a feasibility study to exchange of biomolecules that act as "receptors" in the detection process of complementary DNA. This result is significant because it enables performing the exchange of the detection system from the surface of regeneration besides demonstrating the effectiveness of this proposal work
