In the title crystal, the salt CsMe
2
P(S)NP(S)Me
2
is self-assembled as an undulating supramolecular two-dimensional polymeric structure, poly(μ
4
-tetramethyldithioimidodiphosphinato)caesium, Cs(C
...4
H
12
NP
2
S
2
)
n
, which is parallel to the
bc
plane. The Cs cations are hexacoordinated, being chelated by two thioimidophosphinate groups and two sulfur atoms from neighboring ligands. The anions are linked to the Cs cations by Cs...S and Cs...N electrostatic interactions.
The interaction of the 4,5‐bis(diphenylthiophosphinoyl)‐1,2,3‐triazolate (SPTz−) with different gold surfaces was investigated (nanoparticles, an electrode, and flat sheets). Studies on binding ...affinity of this dithiophosphin‐triazolate on a gold electrode were performed by cyclic voltammetry (CV). Voltammograms exhibit two reductive desorption and only one oxidative readsorption, indicating that once reabsorbed, the molecule achieves a unique conformation. The morphology and average size of modified gold nanoparticles were studied by transmission electron microscopy (TEM) (av. diameter of 5.9 ± 1.8 nm). Further characterization was made by UV‐visible (UV‐vis) spectroscopy showing surface plasmon resonance (SPR) at about 580 nm. The bonding configurations of SPTz− on gold have also been investigated by comparing the FT‐IR and FT‐Raman spectra. The 31P{1H} NMR spectrum of capped nanoparticles exhibited two sharp signals at 30.3 and 29.6 ppm and a very broad signal at 72.7 ppm. X‐ray photoelectron spectroscopy (XPS) showed SPTz− can accomplish a strong interaction with gold nanoparticles through bonds involving a sulfur atom and a nitrogen from the triazole ring with a free terminal PS group, forming self‐assembled monolayers (SAM). This may allow subsequent functionalization through free S/N atoms of the formed SAMs. The SPTz− packing led to a reduction in packing density that permits large spaces between adsorbed headgroups and the inclusion of carbon and oxygen impurities from small molecules; nevertheless, oxidized sulfur or nitrogen species were not detected, indicating the chemical stability of the obtained SAMs.
Suppressed aggregation: The unprecedented alumoxane hydrogensulfide {LAl(SH)}2(μ‐O) and the unique sulfide‐bridged compound {LAl(SH)}2(μ‐S) can be prepared from the easily accessible aluminum ...dihydride LAlH2 (L=HC(CMe)N(2,4,6‐Me3C6H2)2−). Owing to the cis conformation of the terminal SH groups, these compounds represent ideal precursors for the synthesis of heterometallic compounds.
We report the synthesis of the first main group complexes involving the ephedrinedithiocarbamate ligand, the X-ray single crystal structure of two of the complexes were determined, showing two ...different coordination modes. Antibacterial assays were done and DFT calculations were used to explain the antibacterial activity.
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The synthesis of five new complexes involving the ephedrinedithiocarbamate ligand (ephedtc) with group 13 and 15 metals (III) is reported. Complexes As(ephedtc)3 (1), Sb(ephedtc)3 (2), Bi(ephedtc)3 (3), and In(ephedtc)3 (5) were obtained from the ephedrinedithiocarbamate sodium salt Na(ephedtc) and the corresponding trichlorides MCl3, whereas for Ga(ephedtc)3, (4) Ga(NO3)3 was used. All compounds were characterized by elemental analyses, IR, mass spectrometry (FAB+) and 1H and 13C NMR. In addition, single crystal structures of 2 and 5 were obtained showing two different coordination modes for the dithiocarbamate moiety, an anisobidentate coordination mode for 2 and an isobidentate coordination for 5 that generates a propeller-type structure. Compound 2 shows a distorted trigonal antiprismatic geometry around the metal atom while in 5 a distorted octahedral geometry is observed. Additionally, the crystalline structure of the ionic pair ephedrinium ephedrinedithiocarbamate (6) was determined. Antibacterial assay showed that 5 was the most active against ATCC bacterial strains and clinical isolate E. coli BLE (MIC 14.6–29.9µM), and 3 against MRS strains (MIC 1.7 and 13.4µM). The chemical hardness concept and the location of the HOMO and LUMO frontier orbitals on the molecular structures of 1–5 were employed to explain its particular antibacterial activity, using the DFT calculations.
•Self-assembly of the dithiophosphonate tectons generating supramolecular synthons via NH···S, NH···O, CH···S, CH···O, CH···π, and lp···π interactions.•Connection between molecular and supramolecular ...chirality in the crystalline state (chirogenesis).•NCI index analysis supports the proposition of P-stereogenic centers.•Chiral transference of the p atom to the supramolecular helical assembly.•Spontaneous resolution process to generate the homochiral crystal.
The self-assembly of the dithiophosphonate tectons synthesized in this work generated novel supramolecular synthonsvia NH···S, NH···O, CH···S, CH···O, CH···π, and lp···π interactions. The reaction of the salts with chloro dithiastibocanes X(CH2CH2S)2SbCl (X = O, S) led to the formation of coordination compounds in which the crystal structures showed two new supramolecular synthons stabilized by CH···π and lp···π interactions. The theoretical study of the electronic density of the crystal and their synthons in the solid-state used the robust NCI index to confirm the nature of the interactions found. This study confirmed the connection between molecular and supramolecular chirality in the crystalline state. Three significant features unequivocally support the findings: the role of intramolecular interactions, the electronic density differences among diastereomers, and the nature of trans-annular bonds. The characterization of the salts: ammonium-menthoxy (4-methoxyphenyl) dithiophosphonate (1), triethylammonium-menthoxy (4-methoxyphenyl)-dithiophosphonate (2), triethylammonium-biphenyl-4‑methoxy (4-methoxyphenyl) dithiophosphonate (3), and the coordination compounds O(CH2CH2S)2SbS2P(biphenyl-4‑methoxy)(4-MeOC6H4) (4) and S(CH2CH2S)2SbS2P(biphenyl-4‑methoxy)(4-MeOC6H4) (5) was carried out by elemental analyses, IR, NMR (1H, 13C, 31P), and single-crystal X-ray diffraction analysis.
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•Three lanthanum(III) 2-amino-1-cyclopentene-1-carbodiothioate (ACDA) were obtained.•It is reported the first structural determinations of a rare earth ACDA complexes.•The ACDA is bonded to the ...lanthanum in a S,S coordination mode.•The DFT calculations for all the ACDA lanthanide complexes is in favor of the S,S mode.
The synthesis and characterization of the first three La(III) 2-amino-1-cyclopentene-1-carbodithioate (ACDA) complexes is reported including two ionic complexes, NEt3HLa(ACDA4) (1), N(n-Bu)4La(ACDA4 (2) and La(ACDA)3)(1,10-phenanthroline) (3). The single-crystal X-ray structures of 1–3 correspond to the first known structural determination of ACDA rare earth complexes. Compounds 1–3 show an S,S coordination mode, and due to hydrogen bonding present in the ligands, secondary interactions were observed. DFT calculations for all the lanthanide series indicate that the ACDA ligand binds in an isobidentate fashion through low covalent M–S bonds, as evidenced by natural population analysis. Furthermore, the S,S coordination mode is overwhelmingly preferred over the N,S coordination, as demonstrated by free energy calculations from the vibrational frequency analysis.
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The alkaline earth metal complex Mg{4,5‐(P(S)Ph2)2}2tz}2(thf)4 (2) and the bimetallic complexes, M{4,5‐(P(S)Ph2)2}2tz}2(thf)2 M = Ca (3), Sr (4), Ba (5), SrI{4,5‐(P(S)Ph2)2tz}2(thf)32 (6), and ...{BaI(4,5‐(P(S)Ph2)2tz)}2(thf)7 (7) were prepared in good yields from the metathesis reactions of the potassium salt of 4,5‐bis(diphenylthiophosphoranyl)‐1,2,3‐triazole H{4,5‐(P(S)Ph2)2tz} (1) and MI2 (M = Ca, Sr, Ba), whereas the tetrametallic magnesium hydroxide Mg2(μ‐OH){4,5‐(P(S)Ph2)2}2tz}32 (8) was obtained as the hydrolysis product from the starting material (MgnBuCl) and 1. The NMR study of 2–8 in solution suggests the formation of solvated species in CD3OD‐d4, whereas for 4, 5, and 6 a fluxional behavior is observed in CD2Cl2. The structural analyses of 3–5, 6, and 7 in solid state reveal in all cases a central core defined by M2N4 heterocycle bearing M–S bonding. The degree of aggregation observed for these compounds depends significantly on the size of the metal atom as well as on the metal‐ligand molar ratio employed for each reaction.
Six new diorganotin (IV) complexes, Ph
Sn(Pr-ACDA)
, Bu
Sn(Pr-ACDA)
, Ph
Sn(Bz-ACDA)
, Bu
Sn(Bz-ACDA)
, Me
Sn(Bz-ACDA)
, t-Bu
Sn(Bz-ACDA)
are reported (where ACDA is the ...2-amino-1-cyclopentene-1-carbodithioic anion). The diorganotin complexes were prepared from reactions between sodium N-propyl and N-benzyl-2-amino-1-cyclopentene-1-carbodithioate with R
SnCl
(R=Ph, Bu, Me, tBu) in a 2:1 ratio. All complexes were characterized by elemental analysis, IR, multinuclear NMR (
H,
C, and
Sn), FAB
mass spectrometry and in the case of
,
and
by single-crystal X-ray diffraction. Both solution and solid state studies show that dithioacid ligands are coordinated to tin in an aniso-bidentate manner. In all complexes coordination takes place only through the carbodithioate moieties.
Sn NMR data indicate pentacoordination of tin in solution. The tin coordination geometry, in all three structures is a highly distorted octahedral geometry, where tin is bonded to the four sulfur atoms of the two aniso-bidentate carbodithioate ligands in the equatorial plane and the organic substituents on tin atom in
-positions. In addition, the crystal structures show the presence of N-H…S hydrogen bonding contacts.
•Metallo inorganic rings of Sc, Y, La, Lu, into a phosphazenic ligand.•Structural comparison of Sc, Y, La, and Lu complexes•The flexibility of phosphazenic ligands in rare earth complexes.•Inorganic ...rings containing rare earth cations.•Influence of the ionic radii in the structure of rare earth complexes.
In the present study, we report the synthesis, spectroscopic characterization, and X-ray single crystal structural determination of four rare earth complexes, MPh2P(O)NP(O)PPh23, M = Sc, Y, La, and Lu. The structural study reveals that the Sc, Y, and Lu complexes have coordination numbers of six, while the La complex shows a coordination number of seven, through the presence of the additional coordination of a water molecule with a square-face-capped geometry, where the water molecule enables the formation of a dimeric structure through O-H...O hydrogen bond interactions. The metal ions M3+, Sc, Y, La, and Lu are coordinated to the Ph2P(O)NP(O)Ph2− ligand with a delocalized phosphazenic PNP system in an O,O isobidentate manner, generating carbon-free metallo-inorganic six-membered rings, of which one acquires the a (anti-parallel) conformation and the other two the twist-boat conformation. The Y and Lu complexes crystallized with similar unit cells, M...O distances, and O...M...O angles that are consequences of their similar crystal radii related to the lanthanide contraction in Lu, while the La complex has a coordination number of seven through the coordination of a water molecule and a square-face-capped geometry. The O-M-O angles in the complexes suggest that the bite of the ligand depends on the size of the metal ion, the flexibility, and the steric effects of the tetra-phenyl-imidodiphosphinate ligand.
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•Tetrazole-carboxylates of organotin(IV) were obtained for first occasion.•The reaction of Bargellini is a useful technique for the preparation of new ligands.•Tetrazole-carboxylate complexes have a ...rigid tetrazole and a flexible carboxylate.•X-Ray structures of four organotin(IV) tetrazole-carboxylates were determinated.
The organometallic tin(IV) carboxylates are, in general, well known; however, the corresponding organotin(IV) tetrazole-carboxylates are not known, despite their interest in function of the presence, in these bifunctional ligands, of a rigid tetrazole ring and a flexible carboxylate anion with the possibility of a wide structural diversity and relevant biological activity. In consequence, we report here the synthesis and full characterization of seven new organotin(IV) complexes with a 5-thio-tetrazole carboxylate ligand, the anion of the 2-methyl-2-(1-phenyl-1H-tetrazol-5-yl)sulfanyl)-propanoic acid obtained from the Bargellini reaction. The reaction of Bargellini is a source of economical synthesis of compounds in a multi-component reaction with an increase in complexity and functionality; however, its use in the synthesis of ligands for the obtention of new metal complexes is very limited. Therefore, another reason for this study lies in the convenience of broadly showing the usefulness of this reaction in the synthesis of ligands suitable for coordination chemistry. The new complexes were characterized by common spectroscopic techniques, and elemental analysis, and four of the complexes by single-crystal X-ray diffraction, whose structures are discussed, and the complexes were tested for their antibacterial capacities.
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