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Gregory J Grant - One of the best experts on this subject based on the ideXlab platform.
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interaction with calf thymus dna and photoinduced cleavage of pbr322 by rhodium iii and iridium iii complexes containing Crown Thioether ligands
Inorganica Chimica Acta, 2018Co-Authors: Ashley D Cardenal, Gregory J Grant, Hendrik J Greve, Weinan Chen, Hitesh Vashi, Titus V AlbuAbstract:Abstract In this report, we present our investigation on the photoinduced cleavage of plasmid pBR322 and the binding interactions with calf-thymus (CT) DNA by a series of Thioether metal complexes. The complexes of interest are rhodium and iridium complexes containing thiaCrown ligands 1,4,7-trithiacyclononane (9S3) and 1-oxa-4,7-dithiacyclononane (9S2O), and the complexes are abbreviated as [Rh(9S3)Cl3], [Rh(9S2O)Cl3], and [Ir(9S3)Cl3]. In the nicking assay, pBR322 was treated with each complex and irradiated at 254 and 350 nm, respectively, in concentration- and time-dependent studies. The nicking assay revealed that, under exposure to 254-nm radiation, [Rh(9S3)Cl3] and [Rh(9S2O)Cl3] cleaved pBR322 efficiently forming a nicked form, while [Ir(9S3)Cl3] was least efficient. For the 350-nm irradiation, a similar trend was observed, with [Rh(9S3)Cl3] being the most efficient one, however with a lower efficiency than at 254 nm. An ethidium bromide displacement assay was also carried out to evaluate the binding interaction of each compound with CT-DNA by titrating the pre-equilibrated complex of CT-DNA and EB with the investigated complexes. The efficient concentration to achieve a 50% loss in fluorescent emission was found to be 24 μM for [Rh(9S3)Cl3] and 35 μM for [Rh(9S2O)Cl3], while [Ir(9S3)Cl3] was an ineffective DNA binder.
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Contrasting arsine and phosphine coordination behaviour: heteroleptic palladium(II) complexes with triphenylarsine and a Crown Thioether
Main Group Chemistry, 2007Co-Authors: Gregory J Grant, Desirée A. Biggers, Don VanderveerAbstract:The synthesis, spectroscopic data and crystal structures of two new mononuclear Pd(II) heteroleptic complexes with the Crown triThioether 1,4,7-trithiacyclononane (9S3) and the arsine ligand, triphenylarsine (AsPh3) are presented. Reaction between [Pd(9S3)Cl2] and AsPh3 (1:2 stoichiometry) in nitromethane followed by metathesis to the hexafluorophosphate salt results in the formation of two different palladium(II) complexes, the expected bis arsine complex [Pd(9S3)(AsPh3)2](PF6)2 as well as, surprisingly, the intermediate mono arsine-chloro complex [Pd(9S3)(AsPh3)(Cl)](PF6). Both complexes exhibit the anticipated structure consisting of a cis square planar array of two sulfur atoms from the 9S3 and either two As donors (bis AsPh3 complex) or one As and one Cl donor (mono AsPh3 complex). The third 9S3 sulfur atom exhibits a long distance interaction with the palladium forming an elongated square pyramidal geometry with a coordination environment around the Pd best described as [S2As2 + S1] or [S2AsCl + S1]...
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heteroleptic platinum ii complexes with Crown Thioether and phosphine ligands the crystal structures of pt 9s3 pph3 cl pf6 ch3no2 and pt 10s3 pph3 cl pf6
Polyhedron, 2002Co-Authors: Gregory J Grant, David F Galas, Don VanderveerAbstract:Abstract We wish to report the synthesis, spectroscopic properties, and crystal structures of two Pt(II) heteroleptic complexes with triphenylphosphine (PPh3), chloride, and the Crown triThioethers 9S3 (1,4,7-trithiacyclononane) or 10S3 (1,4,7-trithiacyclodecane). Both complexes have the general formula [Pt(L)(PPh3)Cl](PF6) (L=9S3 or 10S3) and form similar structures in which the Pt(II) center is surrounded by a cis arrangement of the chloride, the P donor from the phosphine, and two sulfur atoms from the 9S3 ligand. The third sulfur in each structure forms a longer interaction with the platinum resulting in an elongated square pyramidal structure. The 195Pt NMR chemical shifts for both complexes show a value near −4100 ppm, consistent with a cis-PtS2PCl coordination sphere. The triThioethers in both complexes are fluxional, resulting in relatively simple 13C NMR spectra for them (9S3, one line; 10S3, four lines). Although the fluxional behavior of the 9S3 ligand in platinum group metal complexes is well-documented, our NMR and structural data confirm definite fluxional behavior of the 10S3 ligand for the first time.
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synthetic electrochemical and structural studies on heterobimetallic Crown Thioether complexes with group 10 metals the crystal structures of pt 9s3 dppf pf6 2 ch3no2 and pd 9s3 dppf pf6 2 ch3no2
Journal of Organometallic Chemistry, 2001Co-Authors: Gregory J Grant, Shawn M Carter, Lebron A Russell, Ivan M Poullaos, Don VanderveerAbstract:Abstract The syntheses, electrochemistry, and crystal structures for two new Pt(II) and Pd(II) heteroleptic bimetallic complexes with the Crown triThioether 1,4,7-trithiacyclononane (9S3) and the diphosphine ligand, 1,1′-bis(diphenylphosphino)ferrocene (dppf) are reported. Both complexes have the general formula [M(9S3)(dppf)](PF6)2 (M=Pt or Pd) and exhibit the anticipated structure forming a distorted cis square planar array of two sulfur atoms from the 9S3 and two phosphorus atoms. These are, to our knowledge, the first reported examples of dppf transition metal complexes involving a Thioether as the ancillary ligand. The dppf ligand functions as a bidentate chelator to a single metal center, and the third 9S3 sulfur atom does interact with the metal ion from a greater distance (PtS=2.8167(8) A; PdS=2.7916(5) A) to yield an elongated square pyramidal geometry. The two structures are isomorphous with very similar bond distances and angles. The values for the 31P-NMR chemical shifts (Pt=15.09 ppm, Pd=−0.47 ppm), the 195Pt-NMR chemical shift for the Pt(II) complex (−4353 ppm) and 1J(195Pt–31P) coupling constants (3511 Hz) are all consistent with a cis-MS2P2 square planar coordination sphere. The 9S3 ligand is fluxional in solution for both complexes. The electrochemistry of both complexes is dominated by a reversible Fe(II)/Fe(III) couple from the ferrocene moiety (E1/2=+721 mV for Pt(II), +732 mV for Pd(II), both versus Fc/Fc+).
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synthesis and complexation studies of mesocyclic and macrocyclic polyThioethers xiv Crown Thioether complexes of palladium ii and platinum ii
Inorganica Chimica Acta, 1996Co-Authors: Gregory J Grant, Nathan J Spangler, William N Setzer, Don Vanderveer, Larry F MehneAbstract:Abstract This paper describes the synthesis and characterization of several Crown Thioether complexes of Pt(II) and Pd(II). We wish to report the syntheses and X-ray crystal structures of both the Pd(II) and Pt(II) complexes with the macrocyclic Thioether complex, 1,4,7,11,14,17-hexathiacycloeicosane (20S6). Crystal data for [Pd(20S6)](PF6)2: C14H28F12P2PdS6; monoclinic, space group P2 1 c ; a = 12.910(3) A , b = 9.810(20) A , c = 22.103(6) A , β = 102.170(20)°, V = 2700.39 A 3 ; Z = 4; R = 0.055; D = 1.931 g cm −3 ; 6346 reflections measured. Crystal data for [Pt(20S6)](PF6)2·CH3NO2: C15H31F12NO2P2PtS6; monoclinic, space group Cc; a = 12.321(5) A , b = 14.608(7) A , c = 17.032(5) A ; β = 98.15(3)°, V= 3034.55 A 3 ; Z= 4; R = 0.036; D = 2.045 g cm −3 ; 2777 reflections measured. Neither complex exhibits any significant electrochemistry or any visible absorption bands. Both complexes crystallize in the same linkage isomer where the metal ion is surrounded by a distorted square planar arrangement of four sulfur atoms. Two sulfur atoms that are adjacent to each other in the macrocyclic ring remain uncoordinated. 13C NMR spectroscopy reveals the presence of additional isomers in solution. We also wish to report the synthesis and X-ray crystal structure of the Crown Thioether complex, bis(1,4,7-trithiacyclodecane)platinum(II) hexafluorophosphate, [Pt(10S3)2](PF6)2. The two 10S3 ligands are arranged around the platinum in pseudooctahedral fashion to yield the meso stereoisomer. Four of the six sulfur atoms from the 10S3 ligands form a square planar arrangement around the platinum (mean Pt-Sequatorial bond distance = 2.30 A). The remaining two sulfurs are coordinated axially at a much greater distance from the Pt (Pt-Saxial = 3.21 A). Crystal data for [Pt(10S3)2](PF6)2·2CH3NO2: C16H34PdS6P2F12N2O4; monoclinic, space group C2 c ; a = 22.473(9) A , b = 12.071(4) A , c = 11.186(3) A ; β = 94.14(3)°, V= 3026.53 A 3 ; Z = 4; R = 0.046; D = 1.991 g cm −3 ; 2836 reflections measured. Cyclic voltammetry measured in acetonitrile showed a single, reversible oxidation wave at +0.324 V versus F c F c + . Variable temperature 13C NMR spectroscopy shows no solvent-complex interactions, in contrast to the Pd(II) analog. The palladium(II) complex, [Pd(ttn)2](PF6)2, which contains the acyclic Thioether 2,5,8-trithianonane (ttn) was also prepared.
Don Vanderveer - One of the best experts on this subject based on the ideXlab platform.
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Contrasting arsine and phosphine coordination behaviour: heteroleptic palladium(II) complexes with triphenylarsine and a Crown Thioether
Main Group Chemistry, 2007Co-Authors: Gregory J Grant, Desirée A. Biggers, Don VanderveerAbstract:The synthesis, spectroscopic data and crystal structures of two new mononuclear Pd(II) heteroleptic complexes with the Crown triThioether 1,4,7-trithiacyclononane (9S3) and the arsine ligand, triphenylarsine (AsPh3) are presented. Reaction between [Pd(9S3)Cl2] and AsPh3 (1:2 stoichiometry) in nitromethane followed by metathesis to the hexafluorophosphate salt results in the formation of two different palladium(II) complexes, the expected bis arsine complex [Pd(9S3)(AsPh3)2](PF6)2 as well as, surprisingly, the intermediate mono arsine-chloro complex [Pd(9S3)(AsPh3)(Cl)](PF6). Both complexes exhibit the anticipated structure consisting of a cis square planar array of two sulfur atoms from the 9S3 and either two As donors (bis AsPh3 complex) or one As and one Cl donor (mono AsPh3 complex). The third 9S3 sulfur atom exhibits a long distance interaction with the palladium forming an elongated square pyramidal geometry with a coordination environment around the Pd best described as [S2As2 + S1] or [S2AsCl + S1]...
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heteroleptic platinum ii complexes with Crown Thioether and phosphine ligands the crystal structures of pt 9s3 pph3 cl pf6 ch3no2 and pt 10s3 pph3 cl pf6
Polyhedron, 2002Co-Authors: Gregory J Grant, David F Galas, Don VanderveerAbstract:Abstract We wish to report the synthesis, spectroscopic properties, and crystal structures of two Pt(II) heteroleptic complexes with triphenylphosphine (PPh3), chloride, and the Crown triThioethers 9S3 (1,4,7-trithiacyclononane) or 10S3 (1,4,7-trithiacyclodecane). Both complexes have the general formula [Pt(L)(PPh3)Cl](PF6) (L=9S3 or 10S3) and form similar structures in which the Pt(II) center is surrounded by a cis arrangement of the chloride, the P donor from the phosphine, and two sulfur atoms from the 9S3 ligand. The third sulfur in each structure forms a longer interaction with the platinum resulting in an elongated square pyramidal structure. The 195Pt NMR chemical shifts for both complexes show a value near −4100 ppm, consistent with a cis-PtS2PCl coordination sphere. The triThioethers in both complexes are fluxional, resulting in relatively simple 13C NMR spectra for them (9S3, one line; 10S3, four lines). Although the fluxional behavior of the 9S3 ligand in platinum group metal complexes is well-documented, our NMR and structural data confirm definite fluxional behavior of the 10S3 ligand for the first time.
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synthetic electrochemical and structural studies on heterobimetallic Crown Thioether complexes with group 10 metals the crystal structures of pt 9s3 dppf pf6 2 ch3no2 and pd 9s3 dppf pf6 2 ch3no2
Journal of Organometallic Chemistry, 2001Co-Authors: Gregory J Grant, Shawn M Carter, Lebron A Russell, Ivan M Poullaos, Don VanderveerAbstract:Abstract The syntheses, electrochemistry, and crystal structures for two new Pt(II) and Pd(II) heteroleptic bimetallic complexes with the Crown triThioether 1,4,7-trithiacyclononane (9S3) and the diphosphine ligand, 1,1′-bis(diphenylphosphino)ferrocene (dppf) are reported. Both complexes have the general formula [M(9S3)(dppf)](PF6)2 (M=Pt or Pd) and exhibit the anticipated structure forming a distorted cis square planar array of two sulfur atoms from the 9S3 and two phosphorus atoms. These are, to our knowledge, the first reported examples of dppf transition metal complexes involving a Thioether as the ancillary ligand. The dppf ligand functions as a bidentate chelator to a single metal center, and the third 9S3 sulfur atom does interact with the metal ion from a greater distance (PtS=2.8167(8) A; PdS=2.7916(5) A) to yield an elongated square pyramidal geometry. The two structures are isomorphous with very similar bond distances and angles. The values for the 31P-NMR chemical shifts (Pt=15.09 ppm, Pd=−0.47 ppm), the 195Pt-NMR chemical shift for the Pt(II) complex (−4353 ppm) and 1J(195Pt–31P) coupling constants (3511 Hz) are all consistent with a cis-MS2P2 square planar coordination sphere. The 9S3 ligand is fluxional in solution for both complexes. The electrochemistry of both complexes is dominated by a reversible Fe(II)/Fe(III) couple from the ferrocene moiety (E1/2=+721 mV for Pt(II), +732 mV for Pd(II), both versus Fc/Fc+).
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synthesis and complexation studies of mesocyclic and macrocyclic polyThioethers xiv Crown Thioether complexes of palladium ii and platinum ii
Inorganica Chimica Acta, 1996Co-Authors: Gregory J Grant, Nathan J Spangler, William N Setzer, Don Vanderveer, Larry F MehneAbstract:Abstract This paper describes the synthesis and characterization of several Crown Thioether complexes of Pt(II) and Pd(II). We wish to report the syntheses and X-ray crystal structures of both the Pd(II) and Pt(II) complexes with the macrocyclic Thioether complex, 1,4,7,11,14,17-hexathiacycloeicosane (20S6). Crystal data for [Pd(20S6)](PF6)2: C14H28F12P2PdS6; monoclinic, space group P2 1 c ; a = 12.910(3) A , b = 9.810(20) A , c = 22.103(6) A , β = 102.170(20)°, V = 2700.39 A 3 ; Z = 4; R = 0.055; D = 1.931 g cm −3 ; 6346 reflections measured. Crystal data for [Pt(20S6)](PF6)2·CH3NO2: C15H31F12NO2P2PtS6; monoclinic, space group Cc; a = 12.321(5) A , b = 14.608(7) A , c = 17.032(5) A ; β = 98.15(3)°, V= 3034.55 A 3 ; Z= 4; R = 0.036; D = 2.045 g cm −3 ; 2777 reflections measured. Neither complex exhibits any significant electrochemistry or any visible absorption bands. Both complexes crystallize in the same linkage isomer where the metal ion is surrounded by a distorted square planar arrangement of four sulfur atoms. Two sulfur atoms that are adjacent to each other in the macrocyclic ring remain uncoordinated. 13C NMR spectroscopy reveals the presence of additional isomers in solution. We also wish to report the synthesis and X-ray crystal structure of the Crown Thioether complex, bis(1,4,7-trithiacyclodecane)platinum(II) hexafluorophosphate, [Pt(10S3)2](PF6)2. The two 10S3 ligands are arranged around the platinum in pseudooctahedral fashion to yield the meso stereoisomer. Four of the six sulfur atoms from the 10S3 ligands form a square planar arrangement around the platinum (mean Pt-Sequatorial bond distance = 2.30 A). The remaining two sulfurs are coordinated axially at a much greater distance from the Pt (Pt-Saxial = 3.21 A). Crystal data for [Pt(10S3)2](PF6)2·2CH3NO2: C16H34PdS6P2F12N2O4; monoclinic, space group C2 c ; a = 22.473(9) A , b = 12.071(4) A , c = 11.186(3) A ; β = 94.14(3)°, V= 3026.53 A 3 ; Z = 4; R = 0.046; D = 1.991 g cm −3 ; 2836 reflections measured. Cyclic voltammetry measured in acetonitrile showed a single, reversible oxidation wave at +0.324 V versus F c F c + . Variable temperature 13C NMR spectroscopy shows no solvent-complex interactions, in contrast to the Pd(II) analog. The palladium(II) complex, [Pd(ttn)2](PF6)2, which contains the acyclic Thioether 2,5,8-trithianonane (ttn) was also prepared.
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Crown Thioether complexes of trivalent transition metal ions the crystal structure of cr 18s6 cl3
Inorganica Chimica Acta, 1995Co-Authors: Gregory J Grant, William N Setzer, Karen E Rogers, Don VanderveerAbstract:Abstract The structure of the macrocyclic complex, [Cr(18S6)Cl 3 ] (18S6=1,4,7,10,13,16-hexathiacyclooctadecane), has been determined by single-crystal X-ray diffraction, the first Cr(III)-Thioether coordination complex to be structurally characterized. An octahedral environment of three sulfur atoms and three chlorine atoms around the Cr(III) center is observed in the complex, and the stereoisomer obtained in our case is the one in which only three adjacent sulfur atoms in the 18S6 ligand are bonded to the CrCl 3 moiety. This is also the first reported structure of this atypical coordination mode for the 18S6 ligand which typically coordinates in hexadentate fashion or as a bridging ligand. The syntheses, characterization, and electronic spectra of a series of eleven additional Thioether complexes of Cr(III) are described. All twelve Cr complexes have the general formula CrLCl 3 and potentially tetra-, penta- and hexadentate Thioether ligands all function as tridentate ligands coordinating to a single metal center. The electronic spectra for the Cr complexes are all similar and enable ligand field parameters readily to be calculated. The Thioethers function as weak field ligands, and there is a substantial reordering in their spectrochemical series when compared to the series obtained with softer metal ions such as Ni(II) or Fe(II). In addition, the synthesis and characterization of two novel V(III) complexes with the general formula VLCl 3 where L = 1,4,7-trithiacyclononane (9S3) or 1,4,7-trithiacyclodecane (10S3) are described. These are the first two reported examples of Thioether complexes of vanadium(III). The reaction between 9S3 and the anion [Re 2 Cl 8 ] −2 has also been investigated.
George K H Shimizu - One of the best experts on this subject based on the ideXlab platform.
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complexes of the Crown Thioether ligand 2 5 8 trithia 9 o benzenophane tt 9 ob synthesis and molecular structure of cu ncs tt 9 ob
Canadian Journal of Chemistry, 1991Co-Authors: Stephen J Loeb, George K H ShimizuAbstract:The macrocyclic Thioether ligand 2,5,8-trithia[9]-o-benzenophane (TT[9]OB) reacts with [Cu(CH3CN)4][ClO4] to yield the Cu(I) complex [Cu(CH3CN)(TT[9]OB)][ClO4]. The coordinated acetonitrile molecule is displaced by the ambidentate, thiocyanate (NCS)− ion to form the neutral complex [Cu(NCS)(TT[9]OB)] which was characterized by infrared spectroscopy, 1H NMR spectroscopy, and X-ray crystallography. The title complex crystallized in the orthorhombic space group Pbca with a = 14.447(3) A, b = 15.034(4) A, c = 14.851(4) A, V = 3232.2(14) A3, and Z = 8. The structure refined to R = 5.15% and Rw = 5.92% for 1149 reflections with Fo2 > 3σ(Fo2). The Cu(I) ion has a distorted tetrahedral coordination sphere with TT[9]OB occupying three sites while the fourth site is occupied by the thiocyanate ligand which is N-bound to the metal centre. A comparison is made of the molecular conformations of free TT[9]OB and that found for complexed TT[9]OB in [Cu(NCS)(TT[9]OB)] and [Cu(Ph2PMe)(TT[9]OB)][ClO4]. Key words: Thioether...
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copper i and silver i complexes of the Crown Thioether ligand 2 5 8 trithia 9 o benzenophane tt 9 ob structures of cu pph2me tt 9 ob clo4 and ag pph3 tt 9 ob clo4
Inorganic Chemistry, 1991Co-Authors: Broer De Groot, Stephen J Loeb, Garth R Giesbrecht, George K H ShimizuAbstract:The Crown Thioether ligand 2,5,8-trithia[9]-o-benzenophane, TT[9]OB, was prepared in 90−95% yield via the Cs + -mediated cyclization of α,α'-dibromo-o-xylene and 3-thiapentane-1,5-dithiol. This Thioether ligand reacted with [Cu(CH 3 CH) 4 ][ClO 4 ] to give the Cu(I) complex [Cu(CH 3 CN)(TT[9]OB)][ClO 4 ]. The coordinated acetonitrile molecule was displaced by ancillary ligands to form complexes of the formula [Cu(L)(TT[9]OB)][ClO 4 ], where L=benzonitrile, pyridine, PPh 3 , or PPh 2 Me. The complexes were characterized by infrared spectroscopy, 13 C and 1 H NMR spectroscopy, and X-ray crystallography. The complex [Cu-(PPh 2 Me)(TT[9]OB)][ClO 4 ] crystallized in the space group P1
Alexander J Blake - One of the best experts on this subject based on the ideXlab platform.
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influence of Crown Thioether ligands in the structures and of perhalophenyl groups in the optical properties of complexes with argentoaurophilic interactions
Inorganic Chemistry, 2014Co-Authors: Alexander J Blake, Rocio Donamaria, Vito Lippolis, Jose M Lopezdeluzuriaga, Elena Manso, Miguel Monge, Elena M OlmosAbstract:Reaction of [{Au(C6X5)2}Ag]n (X = Cl, F) with the Crown Thioethers 1,4,7-trithiacyclononane ([9]aneS3), 1,4,8,11-tetrathiacyclotetradecane ([14]aneS4), or 1,4,7,10,13,16,19,22-octathiacyclotetracosane ([24]aneS8) affords a series of heteronuclear Au(I)/Ag(I) compounds of stoichiometry [{Au(C6X5)2}Ag(L)x] (L = [9]aneS3, x = 2 (1, 4); L = [14]aneS4, x = 1 (2, 5); L = [24]aneS8, x = 0.5 (3, 6)) formed via Ag-S bonds and Au···Ag contacts. X-ray diffraction studies of some of these complexes reveal different structural arrangements and nuclearity depending on the nature of the Crown Thioether ligand and on the presence or absence of aurophilic interactions. All the complexes are luminescent in the solid state but not in solution. Density functional theory calculations on representative model systems of complexes 2-4 and 6 were carried out to determine the origin of the electronic transitions responsible for their optical properties, which strongly depend on the nature of the perhalophenyl groups bonded to gold.
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metal mediated formation of liquid crystals synthesis structural and thermal analysis of palladium ii complexes of Crown Thioether derivatives
Chemical Communications, 2001Co-Authors: Heiko Richtzenhain, Alexander J Blake, Duncan W Bruce, Ian Andrew Fallis, Martin SchroderAbstract:Oligo(benzoate) derivatives of cis- and trans-(RO)2[14]aneS4, trans-(RO)2[16]aneS4, and their corresponding Pd(II) complexes reveal metal-induced mesomorphic behaviour which can be rationalised by conformational locking of the ligand on complexation.
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a novel alkoxide bridging motif between boron trifluoride and copper ii in a Crown Thioether complex
Chemical Communications, 2000Co-Authors: Liam R Sutton, Alexander J Blake, Paul A Cooke, Martin SchroderAbstract:Reaction of 6-hydroxy-1,4,8,11-tetrathiacyclotetradecane (LH) with Cu(BF4)2 in THF yields [Cu(LH)](BF4)2; crystallisation of the complex from MeNO2/Et2O gives brown crystals of [Cu(LBF3)](BF4), the first example of alkoxide bridging between BF3 and a metal centre.
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cadmium ii bismuth iii lead ii and thallium i Crown Thioether chemistry synthesis and crystal structures of cdi2 2 24 anes8 bicl3 2 24 anes8 pb2 28 anes8 clo4 4 and tl 24 anes8 pf6 24 anes8 1 4 7 10 13 16 19 22 octathiacyclotetracosane 28 anes8 1 4 8 11 15 18 22 25 octathiacyclooctacosane
Journal of The Chemical Society-dalton Transactions, 1998Co-Authors: Alexander J Blake, Vito Lippolis, Dieter Fenske, Martin SchroderAbstract:The complexes [(CdI2)2([24]aneS8)], [(BiCl3)2([24]aneS8)], [Pb2([28]aneS8)][ClO4]4 and [Tl([24]aneS8)]PF6 ([24]aneS8 = 1,4,7,10,13,16,19,22-octathiacyclotetracosane, [28]aneS8 = 1,4,8,11,15,18,22,25-octathiacyclooctacosane) have been prepared, characterized and their crystal structures determined. In [(CdI2)2([24]aneS8)] two CdI2 units are bound to the macrocycle forming a discrete centrosymmetric binuclear complex, Cd(1)–I(1) 2.7551(11), Cd(1)–I(2) 2.6944(8), Cd(1)–S(1) 2.817(2), Cd(1)–S(4) 2.615(2), Cd(1)–S(7) 2.927(2) A. In [(BiCl3)2([24]aneS8)] two BiCl3 units are weakly bonded to the Thioether Crown, Bi–S 3.134(2)–3.313(2) A, to give a discrete centrosymmetric binuclear complex with the two metal centres disposed on opposite sides of the mean plane of the macrocycle. In [Pb2([28]aneS8)][ClO4]4 an S4O4 co-ordination is realized at each PbII sitting in the macrocyclic cavity. The two PbII are bridged by two ClO4– ions, Pb–S 2.861(2)–2.998(2), Pb–O 2.701(7)–2.936(6) A. In contrast, [Tl([24]aneS8)]PF6 adopts a polymeric structure in which each TlI bridges two Thioether Crowns to give an infinite sinusoidal chain. The [S4 + S4] co-ordination sphere at the metal centre is satisfied by two half ligands in a sandwich arrangement, Tl–S 3.2413(11)–3.4734(14) A.
Martin Schroder - One of the best experts on this subject based on the ideXlab platform.
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metal mediated formation of liquid crystals synthesis structural and thermal analysis of palladium ii complexes of Crown Thioether derivatives
Chemical Communications, 2001Co-Authors: Heiko Richtzenhain, Alexander J Blake, Duncan W Bruce, Ian Andrew Fallis, Martin SchroderAbstract:Oligo(benzoate) derivatives of cis- and trans-(RO)2[14]aneS4, trans-(RO)2[16]aneS4, and their corresponding Pd(II) complexes reveal metal-induced mesomorphic behaviour which can be rationalised by conformational locking of the ligand on complexation.
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a novel alkoxide bridging motif between boron trifluoride and copper ii in a Crown Thioether complex
Chemical Communications, 2000Co-Authors: Liam R Sutton, Alexander J Blake, Paul A Cooke, Martin SchroderAbstract:Reaction of 6-hydroxy-1,4,8,11-tetrathiacyclotetradecane (LH) with Cu(BF4)2 in THF yields [Cu(LH)](BF4)2; crystallisation of the complex from MeNO2/Et2O gives brown crystals of [Cu(LBF3)](BF4), the first example of alkoxide bridging between BF3 and a metal centre.
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cadmium ii bismuth iii lead ii and thallium i Crown Thioether chemistry synthesis and crystal structures of cdi2 2 24 anes8 bicl3 2 24 anes8 pb2 28 anes8 clo4 4 and tl 24 anes8 pf6 24 anes8 1 4 7 10 13 16 19 22 octathiacyclotetracosane 28 anes8 1 4 8 11 15 18 22 25 octathiacyclooctacosane
Journal of The Chemical Society-dalton Transactions, 1998Co-Authors: Alexander J Blake, Vito Lippolis, Dieter Fenske, Martin SchroderAbstract:The complexes [(CdI2)2([24]aneS8)], [(BiCl3)2([24]aneS8)], [Pb2([28]aneS8)][ClO4]4 and [Tl([24]aneS8)]PF6 ([24]aneS8 = 1,4,7,10,13,16,19,22-octathiacyclotetracosane, [28]aneS8 = 1,4,8,11,15,18,22,25-octathiacyclooctacosane) have been prepared, characterized and their crystal structures determined. In [(CdI2)2([24]aneS8)] two CdI2 units are bound to the macrocycle forming a discrete centrosymmetric binuclear complex, Cd(1)–I(1) 2.7551(11), Cd(1)–I(2) 2.6944(8), Cd(1)–S(1) 2.817(2), Cd(1)–S(4) 2.615(2), Cd(1)–S(7) 2.927(2) A. In [(BiCl3)2([24]aneS8)] two BiCl3 units are weakly bonded to the Thioether Crown, Bi–S 3.134(2)–3.313(2) A, to give a discrete centrosymmetric binuclear complex with the two metal centres disposed on opposite sides of the mean plane of the macrocycle. In [Pb2([28]aneS8)][ClO4]4 an S4O4 co-ordination is realized at each PbII sitting in the macrocyclic cavity. The two PbII are bridged by two ClO4– ions, Pb–S 2.861(2)–2.998(2), Pb–O 2.701(7)–2.936(6) A. In contrast, [Tl([24]aneS8)]PF6 adopts a polymeric structure in which each TlI bridges two Thioether Crowns to give an infinite sinusoidal chain. The [S4 + S4] co-ordination sphere at the metal centre is satisfied by two half ligands in a sandwich arrangement, Tl–S 3.2413(11)–3.4734(14) A.