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Nadia C. Mösch-zanetti - One of the best experts on this subject based on the ideXlab platform.

  • Bioinspired Tungsten Complexes Employing a Thioether Scorpionate Ligand.
    Inorganic chemistry, 2019
    Co-Authors: Madeleine A. Ehweiner, Carina Vidovič, Ferdinand Belaj, Nadia C. Mösch-zanetti
    Abstract:

    The synthesis and characterization of a series of novel tungsten complexes employing the bioinspired, sulfur-rich Scorpionate Ligand [PhTt] (phenyltris((methylthio)methyl)borate) are reported. Starting from the previously published tungsten precursor [WBr2(CO)3(NCMe)2], a salt metathesis reaction with 1 equiv of Cs[PhTt] led to the desired complex [WBr(CO)3(PhTt)] (1), making it the first tungsten complex employing a poly(thioether)borate Ligand. Surprisingly, the reaction of [WBr2(CO)3(NCMe)2] with an excess of the Ligand gave complex [W(CO)2(η2-CH2SMe)(PhTt)] (2) with a bidentate (methylthio)methanide Ligand as the major product. Thereby, phenyldi((methylthio)methyl)borane is formed, which was isolated and characterized by NMR spectroscopy. The bromido Ligand in [WBr(CO)3(PhTt)] was further substituted by the S,N-bidentate methimazole in order to make the first coordination sphere more sulfur-rich forming [W(CO)2(mt)(PhTt)] (3). Alkyne tungsten complexes employing the sulfur-rich Scorpionate Ligand were accessible by reaction of [WBr2(CO)(C2R2)2(NCMe)] (R = Me, Ph) with Cs[PhTt] forming [WBr(CO)(C2R2)2(PhTt- S, S')] (R = Me 4, Ph 5), with the potentially tridentate Ligand coordinated only via two sulfur atoms. In the case of 4, the higher flexibility of the bidentate coordination leads to the formation of two isomers with respect to the six-membered ring formed by the tungsten center and the two coordinated sulfur atoms of the Ligand. All complexes 1-5 were characterized by single-crystal X-ray diffraction analysis.

  • Mono- and Hexanuclear Zinc Halide Complexes with Soft Thiopyridazine Based Scorpionate Ligands
    Inorganics, 2019
    Co-Authors: Michael Tuchler, Ferdinand Belaj, Melanie Ramböck, Simon Glanzer, Klaus Zangger, Nadia C. Mösch-zanetti
    Abstract:

    Scorpionate Ligands with three soft sulfur donor sites have become very important in coordination chemistry. Despite its ability to form highly electrophilic species, electron-deficient thiopyridazines have rarely been used, whereas the chemistry of electron-rich thioheterocycles has been explored rather intensively. Here, the unusual chemical behavior of a thiopyridazine (6-tert-butylpyridazine-3-thione, HtBuPn) based Scorpionate Ligand towards zinc is reported. Thus, the reaction of zinc halides with tris(6-tert-butyl-3-thiopyridazinyl)borate Na[TntBu] leads to the formation of discrete torus-shaped hexameric zinc complexes [TntBuZnX]6 (X = Br, I) with uncommonly long zinc halide bonds. In contrast, reaction of the sterically more demanding Ligand K[TnMe,tBu] leads to decomposition, forming Zn(HPnMe,tBu)2X2 (X = Br, I). The latter can be prepared independently by reaction of the respective zinc halides and two equiv of HPnMe,tBu. The bromide compound was used as precursor which further reacts with K[TnMe,tBu] forming the mononuclear complex [TnMe,tBu]ZnBr(HPnMe,tBu). The molecular structures of all compounds were elucidated by single-crystal X-ray diffraction analysis. Characterization in solution was performed by means of 1H, 13C and DOSY NMR spectroscopy which revealed the hexameric constitution of [TntBuZnBr]6 to be predominant. In contrast, [TnMe,tBu]ZnBr(HPnMe,tBu) was found to be dynamic in solution.

  • Thiopyridazine-Based Palladium and Platinum Boratrane Complexes.
    Inorganic chemistry, 2018
    Co-Authors: Stefan Holler, Ferdinand Belaj, Michael Tuchler, Beate Gabriele Steller, Luis F. Veiros, Karl Kirchner, Nadia C. Mösch-zanetti
    Abstract:

    Palladium and platinum boratrane complexes of the type [M{B(PnMe,tBu)3}(PPh3)] (M = Pd 1, Pt 2b) have been prepared via the reaction of the soft Scorpionate Ligand potassium tris(4-methyl-6-tert-bu...

  • (Acetamide-κO){2,2′,2′′-boranetriyltris[6-tert-butyl-4-methyl­pyridazine-3(2H)-thione]-κ4B,S,S′,S′′}copper(I) tri­fluoro­methane­sulfonate chloro­form disolvate
    IUCrData, 2018
    Co-Authors: Stefan Holler, Ferdinand Belaj, Nadia C. Mösch-zanetti
    Abstract:

    In the title solvated complex salt, [Cu(C27H39BN6S3)(C2H5NO)](CF3O3S)·2CHCl3, the CuI atom is coordinated by the three S atoms of the pyridazine-3-thione rings in the equatorial plane [Cu—S = 2.3072 (4)–2.3280 (4) A] and the B atom of the Scorpionate Ligand and the O atom of an acetamide Ligand as the apices of a trigonal bipyramid [Cu—B = 2.0456 (16) A and Cu—O = 1.9957 (11) A]. The amide group of the latter Ligand is involved in a bifurcated hydrogen bond to the tri­fluoro­methane­sulfonate anion.

  • {(Hydrogen 2,2′,2′′-boranetri­yl)tris­[6-tert-butyl-4-methyl­pyridazine-3(2H)-thione]-κ3H,S,S′}(tri­phenyl­phosphane-κP)copper(I) chloro­form disolvate
    IUCrData, 2017
    Co-Authors: Stefan Holler, Ferdinand Belaj, Nadia C. Mösch-zanetti
    Abstract:

    In the title complex, [Cu(C27H40BN6S3)(C18H15P)]·2CHCl3, the CuI atom is surrounded in a trigonal-planar arrangement by the tri­phenyl­phosphane Ligand and two of the three S atoms of the Scorpionate Ligand with an additional 3-center–2-electron B—H⋯Cu inter­action, with the H atom as the apex of a pyramid [B—H = 1.140 (17) A and Cu—H = 1.826 (16) A].

Ferdinand Belaj - One of the best experts on this subject based on the ideXlab platform.

  • Bioinspired Tungsten Complexes Employing a Thioether Scorpionate Ligand.
    Inorganic chemistry, 2019
    Co-Authors: Madeleine A. Ehweiner, Carina Vidovič, Ferdinand Belaj, Nadia C. Mösch-zanetti
    Abstract:

    The synthesis and characterization of a series of novel tungsten complexes employing the bioinspired, sulfur-rich Scorpionate Ligand [PhTt] (phenyltris((methylthio)methyl)borate) are reported. Starting from the previously published tungsten precursor [WBr2(CO)3(NCMe)2], a salt metathesis reaction with 1 equiv of Cs[PhTt] led to the desired complex [WBr(CO)3(PhTt)] (1), making it the first tungsten complex employing a poly(thioether)borate Ligand. Surprisingly, the reaction of [WBr2(CO)3(NCMe)2] with an excess of the Ligand gave complex [W(CO)2(η2-CH2SMe)(PhTt)] (2) with a bidentate (methylthio)methanide Ligand as the major product. Thereby, phenyldi((methylthio)methyl)borane is formed, which was isolated and characterized by NMR spectroscopy. The bromido Ligand in [WBr(CO)3(PhTt)] was further substituted by the S,N-bidentate methimazole in order to make the first coordination sphere more sulfur-rich forming [W(CO)2(mt)(PhTt)] (3). Alkyne tungsten complexes employing the sulfur-rich Scorpionate Ligand were accessible by reaction of [WBr2(CO)(C2R2)2(NCMe)] (R = Me, Ph) with Cs[PhTt] forming [WBr(CO)(C2R2)2(PhTt- S, S')] (R = Me 4, Ph 5), with the potentially tridentate Ligand coordinated only via two sulfur atoms. In the case of 4, the higher flexibility of the bidentate coordination leads to the formation of two isomers with respect to the six-membered ring formed by the tungsten center and the two coordinated sulfur atoms of the Ligand. All complexes 1-5 were characterized by single-crystal X-ray diffraction analysis.

  • Mono- and Hexanuclear Zinc Halide Complexes with Soft Thiopyridazine Based Scorpionate Ligands
    Inorganics, 2019
    Co-Authors: Michael Tuchler, Ferdinand Belaj, Melanie Ramböck, Simon Glanzer, Klaus Zangger, Nadia C. Mösch-zanetti
    Abstract:

    Scorpionate Ligands with three soft sulfur donor sites have become very important in coordination chemistry. Despite its ability to form highly electrophilic species, electron-deficient thiopyridazines have rarely been used, whereas the chemistry of electron-rich thioheterocycles has been explored rather intensively. Here, the unusual chemical behavior of a thiopyridazine (6-tert-butylpyridazine-3-thione, HtBuPn) based Scorpionate Ligand towards zinc is reported. Thus, the reaction of zinc halides with tris(6-tert-butyl-3-thiopyridazinyl)borate Na[TntBu] leads to the formation of discrete torus-shaped hexameric zinc complexes [TntBuZnX]6 (X = Br, I) with uncommonly long zinc halide bonds. In contrast, reaction of the sterically more demanding Ligand K[TnMe,tBu] leads to decomposition, forming Zn(HPnMe,tBu)2X2 (X = Br, I). The latter can be prepared independently by reaction of the respective zinc halides and two equiv of HPnMe,tBu. The bromide compound was used as precursor which further reacts with K[TnMe,tBu] forming the mononuclear complex [TnMe,tBu]ZnBr(HPnMe,tBu). The molecular structures of all compounds were elucidated by single-crystal X-ray diffraction analysis. Characterization in solution was performed by means of 1H, 13C and DOSY NMR spectroscopy which revealed the hexameric constitution of [TntBuZnBr]6 to be predominant. In contrast, [TnMe,tBu]ZnBr(HPnMe,tBu) was found to be dynamic in solution.

  • Thiopyridazine-Based Palladium and Platinum Boratrane Complexes.
    Inorganic chemistry, 2018
    Co-Authors: Stefan Holler, Ferdinand Belaj, Michael Tuchler, Beate Gabriele Steller, Luis F. Veiros, Karl Kirchner, Nadia C. Mösch-zanetti
    Abstract:

    Palladium and platinum boratrane complexes of the type [M{B(PnMe,tBu)3}(PPh3)] (M = Pd 1, Pt 2b) have been prepared via the reaction of the soft Scorpionate Ligand potassium tris(4-methyl-6-tert-bu...

  • (Acetamide-κO){2,2′,2′′-boranetriyltris[6-tert-butyl-4-methyl­pyridazine-3(2H)-thione]-κ4B,S,S′,S′′}copper(I) tri­fluoro­methane­sulfonate chloro­form disolvate
    IUCrData, 2018
    Co-Authors: Stefan Holler, Ferdinand Belaj, Nadia C. Mösch-zanetti
    Abstract:

    In the title solvated complex salt, [Cu(C27H39BN6S3)(C2H5NO)](CF3O3S)·2CHCl3, the CuI atom is coordinated by the three S atoms of the pyridazine-3-thione rings in the equatorial plane [Cu—S = 2.3072 (4)–2.3280 (4) A] and the B atom of the Scorpionate Ligand and the O atom of an acetamide Ligand as the apices of a trigonal bipyramid [Cu—B = 2.0456 (16) A and Cu—O = 1.9957 (11) A]. The amide group of the latter Ligand is involved in a bifurcated hydrogen bond to the tri­fluoro­methane­sulfonate anion.

  • Thiopyridazine-Based Palladium and Platinum Boratrane Complexes
    2018
    Co-Authors: Stefan Holler, Ferdinand Belaj, Beate Gabriele Steller, Luis F. Veiros, Karl Kirchner, Michael Tüchler, Nadia C. Mösch-zanetti
    Abstract:

    Palladium and platinum boratrane complexes of the type [M­{B­(PnMe,tBu)3}­(PPh3)] (M = Pd 1, Pt 2b) have been prepared via the reaction of the soft Scorpionate Ligand potassium tris­(4-methyl-6-tert-butyl-3-thiopyridazinyl)­borate KTnMe,tBu with bis­(triphenylphosphine)­metal­(II) dichloride. While reaction with the Pd precursor allowed direct isolation of a symmetric boratrane complex, the Pt analogue led to the hydrido compound [Pt­{B­(PnMe,tBu)3}­(PPh3)­H]Cl (2a), which after reaction with a base gave 2b. Subsequent oxidation with Br2 and I2, respectively, led to the dihalide compounds of the molecular formula [M­{B­(PnMe,tBu)3}­X2] (3a,b–4a,b). Halide abstraction with Ag­(SbF6) further gave interesting cationic compounds of either dimeric [Pd­{B­(PnMe,tBu)3}­X]2(SbF6)2 (5a,b) or monomeric [Pd­{B­(PnMe,tBu)3}­(NCMe)2]­(SbF6) (6) nature. All compounds were spectroscopically and X-ray crystallographically characterized revealing strong metal to boron interactions. DFT calculations of 1, 2a, and 2b confirm the strong M–B interaction and a high positive charge on the metal centers

Michael Tuchler - One of the best experts on this subject based on the ideXlab platform.

  • Mono- and Hexanuclear Zinc Halide Complexes with Soft Thiopyridazine Based Scorpionate Ligands
    Inorganics, 2019
    Co-Authors: Michael Tuchler, Ferdinand Belaj, Melanie Ramböck, Simon Glanzer, Klaus Zangger, Nadia C. Mösch-zanetti
    Abstract:

    Scorpionate Ligands with three soft sulfur donor sites have become very important in coordination chemistry. Despite its ability to form highly electrophilic species, electron-deficient thiopyridazines have rarely been used, whereas the chemistry of electron-rich thioheterocycles has been explored rather intensively. Here, the unusual chemical behavior of a thiopyridazine (6-tert-butylpyridazine-3-thione, HtBuPn) based Scorpionate Ligand towards zinc is reported. Thus, the reaction of zinc halides with tris(6-tert-butyl-3-thiopyridazinyl)borate Na[TntBu] leads to the formation of discrete torus-shaped hexameric zinc complexes [TntBuZnX]6 (X = Br, I) with uncommonly long zinc halide bonds. In contrast, reaction of the sterically more demanding Ligand K[TnMe,tBu] leads to decomposition, forming Zn(HPnMe,tBu)2X2 (X = Br, I). The latter can be prepared independently by reaction of the respective zinc halides and two equiv of HPnMe,tBu. The bromide compound was used as precursor which further reacts with K[TnMe,tBu] forming the mononuclear complex [TnMe,tBu]ZnBr(HPnMe,tBu). The molecular structures of all compounds were elucidated by single-crystal X-ray diffraction analysis. Characterization in solution was performed by means of 1H, 13C and DOSY NMR spectroscopy which revealed the hexameric constitution of [TntBuZnBr]6 to be predominant. In contrast, [TnMe,tBu]ZnBr(HPnMe,tBu) was found to be dynamic in solution.

  • Thiopyridazine-Based Palladium and Platinum Boratrane Complexes.
    Inorganic chemistry, 2018
    Co-Authors: Stefan Holler, Ferdinand Belaj, Michael Tuchler, Beate Gabriele Steller, Luis F. Veiros, Karl Kirchner, Nadia C. Mösch-zanetti
    Abstract:

    Palladium and platinum boratrane complexes of the type [M{B(PnMe,tBu)3}(PPh3)] (M = Pd 1, Pt 2b) have been prepared via the reaction of the soft Scorpionate Ligand potassium tris(4-methyl-6-tert-bu...

  • synthesis and characterization of a thiopyridazinylmethane based Scorpionate Ligand formation of zinc complexes and rearrangement reaction
    Organometallics, 2017
    Co-Authors: Michael Tuchler, Ferdinand Belaj, Stefan Holler, Elke Huber, Susanne Fischer, Daniel A Boese, Nadia C Moschzanetti
    Abstract:

    The Ligand tris(6-tert-butyl-3-thiopyridazinyl)methane ([Tntm]H) was synthesized by the reaction of 6-tert-butyl-3-thiopyridazine with bromoform and reacted with zinc bis(trimethylsilylamide) (Zn(N{SiMe3}2)2) to form [Tntm]Zn(N{SiMe3}2) (1). This complex further reacts with protic and acidic substrates, generating the zinc thiolate complex [Tntm]Zn(StBu) (2) and zinc benzoate complex [Tntm]Zn(O2C-Me2C6H3) (3a). In all compounds [Tntm] was found to have tridentate coordination to the metal center in a κ3-C,N,N fashion, as established by single-crystal X-ray diffraction analyses. In solution, rapid dynamic κ3/κ4 equilibrium occurs at room temperature, while 1H NMR spectroscopy at −30 °C confirms the asymmetric solid-state structure. Furthermore, complex 3a shows a rearrangement reaction in solution where the Ligand isomerizes to give a κ4-C,N,N,S (3b) and a κ4-C,N,S,S isomer (3c), respectively. Density functional theory (DFT) calculations reveal 3b and 3c to be 13.7 and 15.6 kJ/mol more stable in methylene ...

  • zinc Scorpionate complexes with a hybrid thiopyridazinyl thiomethimidazolyl borate Ligand
    European Journal of Inorganic Chemistry, 2016
    Co-Authors: Michael Tuchler, Ferdinand Belaj, Stefan Holler, Sarah Rendl, Natascha Stock, Nadia C Moschzanetti
    Abstract:

    Zinc complexes with the mixed Scorpionate Ligand (6-tert-butyl-3-thiopyridazinyl)bis(2-thiomethimidazolyl)borate (PnBm) have been synthesized and characterized by NMR and IR spectroscopy. The complexes, with the general formula [(PnBm)ZnX]2 [X = Br (1a), I (1b)], are dimeric in the solid state, as determined by single-crystal X-ray diffraction analyses. The zinc atoms are tetrahedrally coordinated by the halogen atom, two sulfur atoms of PnBm, and one sulfur atom from a bridging PnBm Ligand. Variable-temperature 1H NMR spectroscopy indicated dimeric structures also in solution. Upon abstraction of the bromine atom in 1a by thallium triflate, the zinc complex [(PnBm)Zn(OTf)]2 (2) was obtained and fully characterized by 1H and 13C NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction analysis.

  • photoinduced reactivity of the soft hydrotris 6 tert butyl 3 thiopyridazinyl borate Scorpionate Ligand in sodium potassium and thallium salts
    Inorganic Chemistry, 2015
    Co-Authors: Michael Tuchler, Ferdinand Belaj, Georg Raber, Dmytro Neshchadin, Nadia C Moschzanetti
    Abstract:

    The soft Scorpionate Ligand hydrotris(6-tert-butyl-3-thiopyridazinyl)borate (Tn) was found to exhibit pronounced photoreactivity. Full elucidation of this process revealed the formation of 6-tert-butylpyridazine-3-thione (PnH) and 4,5-dihydro-6-tert-butylpyridazine-3-thione (H2PnH). Under exclusion of light, no solvolytic reactions occur, allowing the development of high-yield preparation protocols for the sodium, potassium, and thallium salts and improving the yield for their derived copper boratrane complex. The photoreactivity is relevant for all future studies with electron-deficient Scorpionate Ligands.

Nadia C Moschzanetti - One of the best experts on this subject based on the ideXlab platform.

  • synthesis and characterization of a thiopyridazinylmethane based Scorpionate Ligand formation of zinc complexes and rearrangement reaction
    Organometallics, 2017
    Co-Authors: Michael Tuchler, Ferdinand Belaj, Stefan Holler, Elke Huber, Susanne Fischer, Daniel A Boese, Nadia C Moschzanetti
    Abstract:

    The Ligand tris(6-tert-butyl-3-thiopyridazinyl)methane ([Tntm]H) was synthesized by the reaction of 6-tert-butyl-3-thiopyridazine with bromoform and reacted with zinc bis(trimethylsilylamide) (Zn(N{SiMe3}2)2) to form [Tntm]Zn(N{SiMe3}2) (1). This complex further reacts with protic and acidic substrates, generating the zinc thiolate complex [Tntm]Zn(StBu) (2) and zinc benzoate complex [Tntm]Zn(O2C-Me2C6H3) (3a). In all compounds [Tntm] was found to have tridentate coordination to the metal center in a κ3-C,N,N fashion, as established by single-crystal X-ray diffraction analyses. In solution, rapid dynamic κ3/κ4 equilibrium occurs at room temperature, while 1H NMR spectroscopy at −30 °C confirms the asymmetric solid-state structure. Furthermore, complex 3a shows a rearrangement reaction in solution where the Ligand isomerizes to give a κ4-C,N,N,S (3b) and a κ4-C,N,S,S isomer (3c), respectively. Density functional theory (DFT) calculations reveal 3b and 3c to be 13.7 and 15.6 kJ/mol more stable in methylene ...

  • zinc Scorpionate complexes with a hybrid thiopyridazinyl thiomethimidazolyl borate Ligand
    European Journal of Inorganic Chemistry, 2016
    Co-Authors: Michael Tuchler, Ferdinand Belaj, Stefan Holler, Sarah Rendl, Natascha Stock, Nadia C Moschzanetti
    Abstract:

    Zinc complexes with the mixed Scorpionate Ligand (6-tert-butyl-3-thiopyridazinyl)bis(2-thiomethimidazolyl)borate (PnBm) have been synthesized and characterized by NMR and IR spectroscopy. The complexes, with the general formula [(PnBm)ZnX]2 [X = Br (1a), I (1b)], are dimeric in the solid state, as determined by single-crystal X-ray diffraction analyses. The zinc atoms are tetrahedrally coordinated by the halogen atom, two sulfur atoms of PnBm, and one sulfur atom from a bridging PnBm Ligand. Variable-temperature 1H NMR spectroscopy indicated dimeric structures also in solution. Upon abstraction of the bromine atom in 1a by thallium triflate, the zinc complex [(PnBm)Zn(OTf)]2 (2) was obtained and fully characterized by 1H and 13C NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction analysis.

  • photoinduced reactivity of the soft hydrotris 6 tert butyl 3 thiopyridazinyl borate Scorpionate Ligand in sodium potassium and thallium salts
    Inorganic Chemistry, 2015
    Co-Authors: Michael Tuchler, Ferdinand Belaj, Georg Raber, Dmytro Neshchadin, Nadia C Moschzanetti
    Abstract:

    The soft Scorpionate Ligand hydrotris(6-tert-butyl-3-thiopyridazinyl)borate (Tn) was found to exhibit pronounced photoreactivity. Full elucidation of this process revealed the formation of 6-tert-butylpyridazine-3-thione (PnH) and 4,5-dihydro-6-tert-butylpyridazine-3-thione (H2PnH). Under exclusion of light, no solvolytic reactions occur, allowing the development of high-yield preparation protocols for the sodium, potassium, and thallium salts and improving the yield for their derived copper boratrane complex. The photoreactivity is relevant for all future studies with electron-deficient Scorpionate Ligands.

Stefan Holler - One of the best experts on this subject based on the ideXlab platform.

  • Thiopyridazine-Based Palladium and Platinum Boratrane Complexes.
    Inorganic chemistry, 2018
    Co-Authors: Stefan Holler, Ferdinand Belaj, Michael Tuchler, Beate Gabriele Steller, Luis F. Veiros, Karl Kirchner, Nadia C. Mösch-zanetti
    Abstract:

    Palladium and platinum boratrane complexes of the type [M{B(PnMe,tBu)3}(PPh3)] (M = Pd 1, Pt 2b) have been prepared via the reaction of the soft Scorpionate Ligand potassium tris(4-methyl-6-tert-bu...

  • (Acetamide-κO){2,2′,2′′-boranetriyltris[6-tert-butyl-4-methyl­pyridazine-3(2H)-thione]-κ4B,S,S′,S′′}copper(I) tri­fluoro­methane­sulfonate chloro­form disolvate
    IUCrData, 2018
    Co-Authors: Stefan Holler, Ferdinand Belaj, Nadia C. Mösch-zanetti
    Abstract:

    In the title solvated complex salt, [Cu(C27H39BN6S3)(C2H5NO)](CF3O3S)·2CHCl3, the CuI atom is coordinated by the three S atoms of the pyridazine-3-thione rings in the equatorial plane [Cu—S = 2.3072 (4)–2.3280 (4) A] and the B atom of the Scorpionate Ligand and the O atom of an acetamide Ligand as the apices of a trigonal bipyramid [Cu—B = 2.0456 (16) A and Cu—O = 1.9957 (11) A]. The amide group of the latter Ligand is involved in a bifurcated hydrogen bond to the tri­fluoro­methane­sulfonate anion.

  • Thiopyridazine-Based Palladium and Platinum Boratrane Complexes
    2018
    Co-Authors: Stefan Holler, Ferdinand Belaj, Beate Gabriele Steller, Luis F. Veiros, Karl Kirchner, Michael Tüchler, Nadia C. Mösch-zanetti
    Abstract:

    Palladium and platinum boratrane complexes of the type [M­{B­(PnMe,tBu)3}­(PPh3)] (M = Pd 1, Pt 2b) have been prepared via the reaction of the soft Scorpionate Ligand potassium tris­(4-methyl-6-tert-butyl-3-thiopyridazinyl)­borate KTnMe,tBu with bis­(triphenylphosphine)­metal­(II) dichloride. While reaction with the Pd precursor allowed direct isolation of a symmetric boratrane complex, the Pt analogue led to the hydrido compound [Pt­{B­(PnMe,tBu)3}­(PPh3)­H]Cl (2a), which after reaction with a base gave 2b. Subsequent oxidation with Br2 and I2, respectively, led to the dihalide compounds of the molecular formula [M­{B­(PnMe,tBu)3}­X2] (3a,b–4a,b). Halide abstraction with Ag­(SbF6) further gave interesting cationic compounds of either dimeric [Pd­{B­(PnMe,tBu)3}­X]2(SbF6)2 (5a,b) or monomeric [Pd­{B­(PnMe,tBu)3}­(NCMe)2]­(SbF6) (6) nature. All compounds were spectroscopically and X-ray crystallographically characterized revealing strong metal to boron interactions. DFT calculations of 1, 2a, and 2b confirm the strong M–B interaction and a high positive charge on the metal centers

  • {(Hydrogen 2,2′,2′′-boranetri­yl)tris­[6-tert-butyl-4-methyl­pyridazine-3(2H)-thione]-κ3H,S,S′}(tri­phenyl­phosphane-κP)copper(I) chloro­form disolvate
    IUCrData, 2017
    Co-Authors: Stefan Holler, Ferdinand Belaj, Nadia C. Mösch-zanetti
    Abstract:

    In the title complex, [Cu(C27H40BN6S3)(C18H15P)]·2CHCl3, the CuI atom is surrounded in a trigonal-planar arrangement by the tri­phenyl­phosphane Ligand and two of the three S atoms of the Scorpionate Ligand with an additional 3-center–2-electron B—H⋯Cu inter­action, with the H atom as the apex of a pyramid [B—H = 1.140 (17) A and Cu—H = 1.826 (16) A].

  • synthesis and characterization of a thiopyridazinylmethane based Scorpionate Ligand formation of zinc complexes and rearrangement reaction
    Organometallics, 2017
    Co-Authors: Michael Tuchler, Ferdinand Belaj, Stefan Holler, Elke Huber, Susanne Fischer, Daniel A Boese, Nadia C Moschzanetti
    Abstract:

    The Ligand tris(6-tert-butyl-3-thiopyridazinyl)methane ([Tntm]H) was synthesized by the reaction of 6-tert-butyl-3-thiopyridazine with bromoform and reacted with zinc bis(trimethylsilylamide) (Zn(N{SiMe3}2)2) to form [Tntm]Zn(N{SiMe3}2) (1). This complex further reacts with protic and acidic substrates, generating the zinc thiolate complex [Tntm]Zn(StBu) (2) and zinc benzoate complex [Tntm]Zn(O2C-Me2C6H3) (3a). In all compounds [Tntm] was found to have tridentate coordination to the metal center in a κ3-C,N,N fashion, as established by single-crystal X-ray diffraction analyses. In solution, rapid dynamic κ3/κ4 equilibrium occurs at room temperature, while 1H NMR spectroscopy at −30 °C confirms the asymmetric solid-state structure. Furthermore, complex 3a shows a rearrangement reaction in solution where the Ligand isomerizes to give a κ4-C,N,N,S (3b) and a κ4-C,N,S,S isomer (3c), respectively. Density functional theory (DFT) calculations reveal 3b and 3c to be 13.7 and 15.6 kJ/mol more stable in methylene ...