bauer spectra suggest the tin atoms to be present in the oxidation state III. The kinetic labilit... more bauer spectra suggest the tin atoms to be present in the oxidation state III. The kinetic lability of the complexes was studied by redistribution reactions between compounds 1 and 3 as well as between 1 and cis-[{2,6-(Me 2 NCH 2) 2 C 6 H 3 SnCl} 2 PdCl 2 ]. DFT calculations provided insights into both the bonding situation of the compounds and the energy difference between the cis and trans isomers. The latter is influenced by the donor strength of the pincer-type ligands.
European Journal of Inorganic Chemistry, Dec 16, 2002
The synthesis and complete characterization by multinuclear NMR, infrared, and Mössbauer spectros... more The synthesis and complete characterization by multinuclear NMR, infrared, and Mössbauer spectroscopy, by single crystal X-ray analysis, as well as by electrospray mass spectrometry of the new soluble triorganotin fluoride Me 2 PhSnF (1) is reported. The crystal structure of 1 reveals a rod-like polymeric structure in the solid state. Solutions of 1 in apolar solvents, such as toluene, contain mixtures of interconvertible oligomers. Ab initio MO calculations on model compounds H 3 SnF, [H 3 SnFSnH 3 ] + , and [FH 3 SnFSnH 3 F] − indicate that the Sn−F bonds are substantially ionic in character, and suggest open-chain species, rather than cyclic species. In donor solvents, such as pyridine, 1 forms complexes with the solvent,
European Journal of Inorganic Chemistry, Dec 9, 2010
The synthesis of the intramolecularly coordinated pentacarbonyltungsten–organostannylene complexe... more The synthesis of the intramolecularly coordinated pentacarbonyltungsten–organostannylene complexes {2,6‐(Me2NCH2)2C6H3}Sn(H)W(CO)5 (2) and [{2,6‐(Me2NCH2)2C6H3}Sn(μ‐OH)W(CO)5]2 (3) and the solid‐state molecular structure of 3, as determined by single‐crystal X‐ray diffraction analysis, are reported. Compound 3 is characterized by hydroxido bridges [Sn–O 2.068(5), 2.231(5) Å], an intramolecular N→Sn coordination bond [2.501(7) Å] and an intramolecular O–H···N hydrogen bond [O···N 2.715(8) Å].
The syntheses and molecular structures of the novel dimeric tin-platinum complex [LSnPtCl2(SMe2)]... more The syntheses and molecular structures of the novel dimeric tin-platinum complex [LSnPtCl2(SMe2)]2 (2), of the novel tin platinum clusters [{LSnPtCl(SMe2)}2SnCl2)] (3), and [(LSn)3(PtCl2)(PtClSnCl)(LSnOHCl)] (6) [L = MeN(CH2CMe2O-)2] and of the unprecedented tin(II) aminoalkoxide-tin oxide chloride complex [O(SnCl)2∙(SnL)2] (5) are reported. The compounds were characterized by multinuclear NMR spectroscopy (1H, 13C, 119Sn, 195Pt), 119Sn Mössbauer spectroscopy (1-3, 6), electrospray ionization mass spectrometry, elemental analyses and single crystal X-ray diffraction analyses (2∙CH2Cl2, 3∙2C4H8O, 5, 6∙3CH2Cl2). The tin(II) aminoalkoxide [MeN(CH2CMe2O)2Sn]2 (1) behaves like a neutral ligand, inserts into a Pt-Cl bond, or is involved in rearrangement reactions with the different behavior occurring even within one compound (3, 6). DFT calculations show that the tin-platinum compounds behave like electronic chameleons.
Reaction between bis(chlorodiphenylstanyl)methane and the sodium salt of 2-hydroxypyridine (pyONa... more Reaction between bis(chlorodiphenylstanyl)methane and the sodium salt of 2-hydroxypyridine (pyONa) in the molar ratio of 1:2 provides the organotin hydroxide derivative [Ph 2 (pyO)SnCH 2 Sn(OH)Ph 2 ] 2 (1) (where pyO = anion of 2-hydroxypyridine), while reaction of bis(dibromophenylstanyl)methane with the sodium salt of pyrimidine-2-thione (pmtNa) in molar ratio of 1:4 gives the corresponding organotin thiolate derivative, as its toluene solvate [BrPh(pmt)Sn] 2 CH 2 AE C 7 H 8 (2) (where pmt = anion of pyrimidine-2-thione). Both compounds were characterized by single crystal X-ray diffraction analysis and contain five-coordinate tin atoms. Compound 1 is a centrosymmetric head-to-tail dimmer with almost symmetrical Sn(1)-O(H)-Sn(2A) bridges.
Five new organotin(IV) molecules with the heterocyclic thioamides; 2-mercaptobenzothiazole (Hmbzt... more Five new organotin(IV) molecules with the heterocyclic thioamides; 2-mercaptobenzothiazole (Hmbzt), 5-chloro-2-mercaptobenzothiazole (Hcmbzt), 3-methyl-2-mercaptobenzothiazole (mmbzt) and 2-mercaptonicotinic acid (H2mna) of formulae [(n-C4H9)2Sn(mbzt)2] (1), [(C6H5)2Sn(mbzt)2] (2), {(CH3)2Sn(cmbzt)2]·1.7(H2O)} (3), [(n-C4H9)2SnCl2(mmbzt)2·(CH2Cl2)] (4) and {[(C6H5)3Sn]2(mna)·[(CH3)2CO]} (5) have been synthesized and characterized by elemental analysis, 1H-, 13C-NMR, FT-IR and Mössbauer spectroscopic techniques. Crystal structures of molecules 1, 3 and 5 have been determined by X-ray diffraction at 173(1) K (1 and 5) and 293(2) K (3). Compound 1 C22H26N2S4Sn, is monoclinic, space group C2/c, a=44.018(2), b=8.8864(5), c=12.8633(7) Å, β=104.195(5)°, Z=8. Compound 3 is also monoclinic, space group P21/c and a=17.128(2) Å, b=17.919(2) Å, c=7.3580(10) Å, β=98.290(10)°, Z=4. In both molecules 1 and 3, two carbon atoms from aryl groups, two sulfur and two nitrogen atoms from thione ligands form a distorted octahedral geometry around tin(IV) with trans-C2, cis-N2, cis-S2 configurations. Compound 5 C45H39NO3SSn2 is monoclinic, space group P21/n, a=9.1148(2) Å, b=29.2819(6), c=15.5556(4) Å, β=106.2851(9)°, Z=4. Complex 5 contains two [(C6H5)3Sn(IV)] moieties linked by a double deprotonated 2-mercaptonicotinic acid (H2mna). Both tin(IV) ions are five coordinated. This complex is the an example of a pentacoordinated Ph3SnXY system with an axial-equatorial arrangement of the phenyl groups at Sn(1) atom. Compounds 1, 3 and 5 were tested for in vitro cytotoxicity against the cancer cell line of sarcoma cells (mesenchymal tissue) from the Wistar rat, polycyclic aromatic hydrocarbons (benzo[a]pyrene) carcinogenesis. Compound 5 exhibits strong cytotoxic activity, while complexes 1 and 3 show less cytotoxic activity.
Zeitschrift für anorganische und allgemeine Chemie, 2010
The syntheses of the arylphosphonic esters 3‐Br‐5‐tBu‐1‐{P(O)(OiPr)2}C6H3 (1), 5‐tBu‐1,3‐{P(O)(Oi... more The syntheses of the arylphosphonic esters 3‐Br‐5‐tBu‐1‐{P(O)(OiPr)2}C6H3 (1), 5‐tBu‐1,3‐{P(O)(OiPr)2}2C6H3 (2), of the heteroleptic intramolecularly coordinated organostannylenes [4‐tBu‐2,6‐{P(O)(OiPr)2}2C6H2]SnX (3, X = Cl; 4, X = Br; 5, X = I; 6, X = SPh), the organoplumbylene [4‐tBu‐2,6‐{P(O)(OiPr)2}2C6H2]PbCl (7), and the transition metal complex [4‐tBu‐2,6‐{P(O)(OiPr)2}2C6H2]Sn(Cl)Cr(CO)5 (8) are reported. The compounds were characterized by 1H, 13C, 31P, 31P MAS (3), 119Sn, and 119Sn MAS (3) NMR spectroscopy, electrospray ionization mass spectrometry (3), Mössbauer spectroscopy (3–5, 8) and single‐crystal X‐ray diffraction analyses (2, 3–5, 6–8). In contrast to its ethoxy‐substituted analogue [4‐tBu‐2,6‐{P(O)(OEt)2}2C6H2]SnCl, compound 3, like the thiophenolate derivative 6, is monomeric in solution as well as in the solid state. This difference is also manifested by the Mössbauer as well as solid state NMR spectroscopic data. On the other hand, the corresponding organoplumby...
Three novel bicycloazastannoxides, namely, [nBu2Sn(L1)] (1), [nBu2Sn(L2)] (2) and [Bz2Sn(L3)] (3)... more Three novel bicycloazastannoxides, namely, [nBu2Sn(L1)] (1), [nBu2Sn(L2)] (2) and [Bz2Sn(L3)] (3) were synthesized in one pot procedures by reacting diorganotin(IV) precursors with a mixture composed of an α-amino acid with either (E)-2-hydroxy-5-((4-nitrophenyl)diazenyl)benzaldehyde or (E)-2-hydroxy-5-(phenyldiazenyl)benzaldehyde. Single-crystal X-ray diffraction analysis reveal that compound 1 is monomeric, compound 2 consists of both a monomer and a dimer, while compound 3 is a coordination polymer for which two modifications 3A and 3B were identified. The 119Sn NMR chemical shifts measured in CDCl3 solutions indicate five-coordinate tin atoms for 1–3. Further, compounds 1 and 2 were found to be highly selective for sensing hydrogen sulfide in UV/Vis channel in CH3CN/H2O (9:1) media. The development of orange red color is likely the results of a Brønsted-type acid-base reaction of H2S with compounds 1 and 2, respectively, giving di-n-butyltin sulfide and the corresponding pro-lig...
The synthesis, radiolabeling and in vitro evaluation of new silicon-fluoride acceptor (SiFA) deri... more The synthesis, radiolabeling and in vitro evaluation of new silicon-fluoride acceptor (SiFA) derivatized D 2-receptor ligands is reported. The SiFA-technology simplifies the introduction of fluorine-18 into target specific biomolecules for Positron-Emission-Tomography (PET). However, one of the remaining challenges, especially for small molecules such as receptor-ligands, is the bulkiness of the SiFA-moiety. We therefore synthesized four Fallypride SiFA-conjugates derivatized either directly at the benzoic acid ring system (SiFA-DMFP, SiFA-FP, SiFA-DDMFP) or at the butyl-side chain (SiFA-M-FP) and tested their receptor affinities. We found D 2-receptor affinities for all compounds in the nanomolar range (K i(SiFA-DMFP) = 13.6 nM, K i(SiFA-FP) = 33.0 nM,
The incorporation of silicon fluoride acceptor (SiFA) moieties into a variety of molecules, such ... more The incorporation of silicon fluoride acceptor (SiFA) moieties into a variety of molecules, such as peptides, proteins and biologically relevant small molecules, has improved the generation of 18F-radiopharmaceuticals for medical imaging. The efficient isotopic exchange radiofluorination process, in combination with the enhanced [18F]SiFA in vivo stability, make it a suitable strategy for fluorine-18 incorporation. This review will highlight the clinical applicability of [18F]SiFA-labeled compounds and discuss the significant radiotracers currently in clinical use.
bauer spectra suggest the tin atoms to be present in the oxidation state III. The kinetic labilit... more bauer spectra suggest the tin atoms to be present in the oxidation state III. The kinetic lability of the complexes was studied by redistribution reactions between compounds 1 and 3 as well as between 1 and cis-[{2,6-(Me 2 NCH 2) 2 C 6 H 3 SnCl} 2 PdCl 2 ]. DFT calculations provided insights into both the bonding situation of the compounds and the energy difference between the cis and trans isomers. The latter is influenced by the donor strength of the pincer-type ligands.
European Journal of Inorganic Chemistry, Dec 16, 2002
The synthesis and complete characterization by multinuclear NMR, infrared, and Mössbauer spectros... more The synthesis and complete characterization by multinuclear NMR, infrared, and Mössbauer spectroscopy, by single crystal X-ray analysis, as well as by electrospray mass spectrometry of the new soluble triorganotin fluoride Me 2 PhSnF (1) is reported. The crystal structure of 1 reveals a rod-like polymeric structure in the solid state. Solutions of 1 in apolar solvents, such as toluene, contain mixtures of interconvertible oligomers. Ab initio MO calculations on model compounds H 3 SnF, [H 3 SnFSnH 3 ] + , and [FH 3 SnFSnH 3 F] − indicate that the Sn−F bonds are substantially ionic in character, and suggest open-chain species, rather than cyclic species. In donor solvents, such as pyridine, 1 forms complexes with the solvent,
European Journal of Inorganic Chemistry, Dec 9, 2010
The synthesis of the intramolecularly coordinated pentacarbonyltungsten–organostannylene complexe... more The synthesis of the intramolecularly coordinated pentacarbonyltungsten–organostannylene complexes {2,6‐(Me2NCH2)2C6H3}Sn(H)W(CO)5 (2) and [{2,6‐(Me2NCH2)2C6H3}Sn(μ‐OH)W(CO)5]2 (3) and the solid‐state molecular structure of 3, as determined by single‐crystal X‐ray diffraction analysis, are reported. Compound 3 is characterized by hydroxido bridges [Sn–O 2.068(5), 2.231(5) Å], an intramolecular N→Sn coordination bond [2.501(7) Å] and an intramolecular O–H···N hydrogen bond [O···N 2.715(8) Å].
The syntheses and molecular structures of the novel dimeric tin-platinum complex [LSnPtCl2(SMe2)]... more The syntheses and molecular structures of the novel dimeric tin-platinum complex [LSnPtCl2(SMe2)]2 (2), of the novel tin platinum clusters [{LSnPtCl(SMe2)}2SnCl2)] (3), and [(LSn)3(PtCl2)(PtClSnCl)(LSnOHCl)] (6) [L = MeN(CH2CMe2O-)2] and of the unprecedented tin(II) aminoalkoxide-tin oxide chloride complex [O(SnCl)2∙(SnL)2] (5) are reported. The compounds were characterized by multinuclear NMR spectroscopy (1H, 13C, 119Sn, 195Pt), 119Sn Mössbauer spectroscopy (1-3, 6), electrospray ionization mass spectrometry, elemental analyses and single crystal X-ray diffraction analyses (2∙CH2Cl2, 3∙2C4H8O, 5, 6∙3CH2Cl2). The tin(II) aminoalkoxide [MeN(CH2CMe2O)2Sn]2 (1) behaves like a neutral ligand, inserts into a Pt-Cl bond, or is involved in rearrangement reactions with the different behavior occurring even within one compound (3, 6). DFT calculations show that the tin-platinum compounds behave like electronic chameleons.
Reaction between bis(chlorodiphenylstanyl)methane and the sodium salt of 2-hydroxypyridine (pyONa... more Reaction between bis(chlorodiphenylstanyl)methane and the sodium salt of 2-hydroxypyridine (pyONa) in the molar ratio of 1:2 provides the organotin hydroxide derivative [Ph 2 (pyO)SnCH 2 Sn(OH)Ph 2 ] 2 (1) (where pyO = anion of 2-hydroxypyridine), while reaction of bis(dibromophenylstanyl)methane with the sodium salt of pyrimidine-2-thione (pmtNa) in molar ratio of 1:4 gives the corresponding organotin thiolate derivative, as its toluene solvate [BrPh(pmt)Sn] 2 CH 2 AE C 7 H 8 (2) (where pmt = anion of pyrimidine-2-thione). Both compounds were characterized by single crystal X-ray diffraction analysis and contain five-coordinate tin atoms. Compound 1 is a centrosymmetric head-to-tail dimmer with almost symmetrical Sn(1)-O(H)-Sn(2A) bridges.
Five new organotin(IV) molecules with the heterocyclic thioamides; 2-mercaptobenzothiazole (Hmbzt... more Five new organotin(IV) molecules with the heterocyclic thioamides; 2-mercaptobenzothiazole (Hmbzt), 5-chloro-2-mercaptobenzothiazole (Hcmbzt), 3-methyl-2-mercaptobenzothiazole (mmbzt) and 2-mercaptonicotinic acid (H2mna) of formulae [(n-C4H9)2Sn(mbzt)2] (1), [(C6H5)2Sn(mbzt)2] (2), {(CH3)2Sn(cmbzt)2]·1.7(H2O)} (3), [(n-C4H9)2SnCl2(mmbzt)2·(CH2Cl2)] (4) and {[(C6H5)3Sn]2(mna)·[(CH3)2CO]} (5) have been synthesized and characterized by elemental analysis, 1H-, 13C-NMR, FT-IR and Mössbauer spectroscopic techniques. Crystal structures of molecules 1, 3 and 5 have been determined by X-ray diffraction at 173(1) K (1 and 5) and 293(2) K (3). Compound 1 C22H26N2S4Sn, is monoclinic, space group C2/c, a=44.018(2), b=8.8864(5), c=12.8633(7) Å, β=104.195(5)°, Z=8. Compound 3 is also monoclinic, space group P21/c and a=17.128(2) Å, b=17.919(2) Å, c=7.3580(10) Å, β=98.290(10)°, Z=4. In both molecules 1 and 3, two carbon atoms from aryl groups, two sulfur and two nitrogen atoms from thione ligands form a distorted octahedral geometry around tin(IV) with trans-C2, cis-N2, cis-S2 configurations. Compound 5 C45H39NO3SSn2 is monoclinic, space group P21/n, a=9.1148(2) Å, b=29.2819(6), c=15.5556(4) Å, β=106.2851(9)°, Z=4. Complex 5 contains two [(C6H5)3Sn(IV)] moieties linked by a double deprotonated 2-mercaptonicotinic acid (H2mna). Both tin(IV) ions are five coordinated. This complex is the an example of a pentacoordinated Ph3SnXY system with an axial-equatorial arrangement of the phenyl groups at Sn(1) atom. Compounds 1, 3 and 5 were tested for in vitro cytotoxicity against the cancer cell line of sarcoma cells (mesenchymal tissue) from the Wistar rat, polycyclic aromatic hydrocarbons (benzo[a]pyrene) carcinogenesis. Compound 5 exhibits strong cytotoxic activity, while complexes 1 and 3 show less cytotoxic activity.
Zeitschrift für anorganische und allgemeine Chemie, 2010
The syntheses of the arylphosphonic esters 3‐Br‐5‐tBu‐1‐{P(O)(OiPr)2}C6H3 (1), 5‐tBu‐1,3‐{P(O)(Oi... more The syntheses of the arylphosphonic esters 3‐Br‐5‐tBu‐1‐{P(O)(OiPr)2}C6H3 (1), 5‐tBu‐1,3‐{P(O)(OiPr)2}2C6H3 (2), of the heteroleptic intramolecularly coordinated organostannylenes [4‐tBu‐2,6‐{P(O)(OiPr)2}2C6H2]SnX (3, X = Cl; 4, X = Br; 5, X = I; 6, X = SPh), the organoplumbylene [4‐tBu‐2,6‐{P(O)(OiPr)2}2C6H2]PbCl (7), and the transition metal complex [4‐tBu‐2,6‐{P(O)(OiPr)2}2C6H2]Sn(Cl)Cr(CO)5 (8) are reported. The compounds were characterized by 1H, 13C, 31P, 31P MAS (3), 119Sn, and 119Sn MAS (3) NMR spectroscopy, electrospray ionization mass spectrometry (3), Mössbauer spectroscopy (3–5, 8) and single‐crystal X‐ray diffraction analyses (2, 3–5, 6–8). In contrast to its ethoxy‐substituted analogue [4‐tBu‐2,6‐{P(O)(OEt)2}2C6H2]SnCl, compound 3, like the thiophenolate derivative 6, is monomeric in solution as well as in the solid state. This difference is also manifested by the Mössbauer as well as solid state NMR spectroscopic data. On the other hand, the corresponding organoplumby...
Three novel bicycloazastannoxides, namely, [nBu2Sn(L1)] (1), [nBu2Sn(L2)] (2) and [Bz2Sn(L3)] (3)... more Three novel bicycloazastannoxides, namely, [nBu2Sn(L1)] (1), [nBu2Sn(L2)] (2) and [Bz2Sn(L3)] (3) were synthesized in one pot procedures by reacting diorganotin(IV) precursors with a mixture composed of an α-amino acid with either (E)-2-hydroxy-5-((4-nitrophenyl)diazenyl)benzaldehyde or (E)-2-hydroxy-5-(phenyldiazenyl)benzaldehyde. Single-crystal X-ray diffraction analysis reveal that compound 1 is monomeric, compound 2 consists of both a monomer and a dimer, while compound 3 is a coordination polymer for which two modifications 3A and 3B were identified. The 119Sn NMR chemical shifts measured in CDCl3 solutions indicate five-coordinate tin atoms for 1–3. Further, compounds 1 and 2 were found to be highly selective for sensing hydrogen sulfide in UV/Vis channel in CH3CN/H2O (9:1) media. The development of orange red color is likely the results of a Brønsted-type acid-base reaction of H2S with compounds 1 and 2, respectively, giving di-n-butyltin sulfide and the corresponding pro-lig...
The synthesis, radiolabeling and in vitro evaluation of new silicon-fluoride acceptor (SiFA) deri... more The synthesis, radiolabeling and in vitro evaluation of new silicon-fluoride acceptor (SiFA) derivatized D 2-receptor ligands is reported. The SiFA-technology simplifies the introduction of fluorine-18 into target specific biomolecules for Positron-Emission-Tomography (PET). However, one of the remaining challenges, especially for small molecules such as receptor-ligands, is the bulkiness of the SiFA-moiety. We therefore synthesized four Fallypride SiFA-conjugates derivatized either directly at the benzoic acid ring system (SiFA-DMFP, SiFA-FP, SiFA-DDMFP) or at the butyl-side chain (SiFA-M-FP) and tested their receptor affinities. We found D 2-receptor affinities for all compounds in the nanomolar range (K i(SiFA-DMFP) = 13.6 nM, K i(SiFA-FP) = 33.0 nM,
The incorporation of silicon fluoride acceptor (SiFA) moieties into a variety of molecules, such ... more The incorporation of silicon fluoride acceptor (SiFA) moieties into a variety of molecules, such as peptides, proteins and biologically relevant small molecules, has improved the generation of 18F-radiopharmaceuticals for medical imaging. The efficient isotopic exchange radiofluorination process, in combination with the enhanced [18F]SiFA in vivo stability, make it a suitable strategy for fluorine-18 incorporation. This review will highlight the clinical applicability of [18F]SiFA-labeled compounds and discuss the significant radiotracers currently in clinical use.
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Papers by Klaus Jurkschat