scholarly journals Using phosphine ligands with a biological role to modulate reactivity in novel platinum complexes

2018 ◽  
Vol 5 (2) ◽  
pp. 171340 ◽  
Author(s):  
Marcelo Echeverri ◽  
Amparo Alvarez-Valdés ◽  
Francisco Navas ◽  
Josefina Perles ◽  
Isabel Sánchez-Pérez ◽  
...  
Keyword(s):  
Single Crystal ◽  
Platinum Complex ◽  
Platinum Complexes ◽  
Phosphine Ligands ◽  
Biological Role ◽  
Biological Models ◽  
X Ray Diffraction ◽  
X Ray ◽  
Calf Thymus ◽  
The Stability

Three platinum complexes with cis and trans configuration cis -[Pt(TCEP) 2 Cl 2 ], cis -[Pt(tmTCEP) 2 Cl 2 ] and trans -[Pt(TCEP) 2 Cl 2 ], where TCEP is tris(2-carboxyethyl)phosphine, have been synthesized and fully characterized by usual techniques including single-crystal X-ray diffraction for trans -[Pt(TCEP) 2 Cl 2 ] and cis -[Pt(tmTCEP) 2 Cl 2 ]. Here, we also report on an esterification process of TCEP, which takes place in the presence of alcohols, leading to a platinum complex coordinated to an ester tmTCEP (2-methoxycarbonylethyl phosphine) ligand. The stability in solution of the three compounds and their interaction with biological models such as DNA (pBR322 and calf thymus DNA) and proteins (lysozyme and RNase) have also been studied.

scholarly journals Synthesis of Bis(Carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 (n = 0, 1) and Attempt of Synthesis of Gadolinium Bis(Dicarbollide)

Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1321
Author(s):  
Yasunobu Asawa ◽  
Aleksandra V. Arsent’eva ◽  
Sergey A. Anufriev ◽  
Alexei A. Anisimov ◽  
Kyrill Yu. Suponitsky ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Single Crystal ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
X Ray Diffraction ◽  
Stable Conformation ◽  
Acyl Chlorides ◽  
X Ray ◽  
Cesium Fluoride ◽  
The Stability

Bis(carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 (n = 0, 1) were prepared by the reactions of the corresponding carboranyl acyl chlorides with ethylenediamine. Crystal molecular structure of 1,1′-μ-(CH2NH(O)C-1,2-C2B10H11)2 was determined by single crystal X-ray diffraction. Treatment of bis(carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 with ammonium or cesium fluoride results in partial deboronation of the ortho-carborane cages to the nido-carborane ones with formation of [7,7′(8′)-μ-(CH2NH(O)C(CH2)n-7,8-C2B9H11)2]2−. The attempted reaction of [7,7′(8′)-μ-(CH2NH(O)CCH2-7,8-C2B9H11)2]2− with GdCl3 in 1,2-dimethoxy- ethane did not give the expected metallacarborane. The stability of different conformations of Gd-containing metallacarboranes has been estimated by quantum-chemical calculations using [3,3-μ-DME-3,3′-Gd(1,2-C2B9H11)2]− as a model. It was found that in the most stable conformation the CH groups of the dicarbollide ligands are in anti,anti-orientation with respect to the DME ligand, while any rotation of the dicarbollide ligand reduces the stability of the system. This makes it possible to rationalize the design of carborane ligands for the synthesis of gadolinium metallacarboranes on their base.

Synthesis and characterization of the pentazolate anion cyclo-N5ˉ in (N5)6(H3O)3(NH4)4Cl

Science ◽  
2017 ◽  
Vol 355 (6323) ◽  
pp. 374-376 ◽  
Author(s):  
Chong Zhang ◽  
Chengguo Sun ◽  
Bingcheng Hu ◽  
Chuanming Yu ◽  
Ming Lu
Keyword(s):  
Thermal Analysis ◽  
Single Crystal ◽  
Diffraction Analysis ◽  
Decomposition Temperature ◽  
Synthesis And Characterization ◽  
X Ray Diffraction ◽  
X Ray ◽  
Onset Decomposition Temperature ◽  
The Stability

Pentazole (HN5), an unstable molecular ring comprising five nitrogen atoms, has been of great interest to researchers for the better part of a century. We report the synthesis and characterization of the pentazolate anion stabilized in a (N5)6(H3O)3(NH4)4Cl salt. The anion was generated by direct cleavage of the C–N bond in a multisubstituted arylpentazole using m-chloroperbenzoic acid and ferrous bisglycinate. The structure was confirmed by single-crystal x-ray diffraction analysis, which highlighted stabilization of the cyclo-N5ˉ ring by chloride, ammonium, and hydronium. Thermal analysis indicated the stability of the salt below 117°C on the basis of thermogravimetry-measured onset decomposition temperature.

scholarly journals Synthesis, characterization and crystal structure of platinum(II) complexes with thiourea derivative ligands

2018 ◽  
Vol 9 (4) ◽  
pp. 360-368
Author(s):  
Ebru Keskin ◽  
Ummuhan Solmaz ◽  
Gun Binzet ◽  
Ilkay Gumus ◽  
Hakan Arslan
Keyword(s):  
Single Crystal ◽  
Weak Interactions ◽  
Platinum Complexes ◽  
Stacking Interactions ◽  
X Ray Diffraction ◽  
Thiourea Derivatives ◽  
X Ray ◽  
Π Stacking ◽  
Π Stacking Interaction ◽  
In Cis

Thiourea derivatives [N-(di-n-propylcarbamothioyl)-4-fluorobenzamide (HL1) and N-(di-n-propylcarbamothioyl)-4-bromobenzamide (HL2)] and their platinum complexes have been successfully synthesized and structurally characterized by spectroscopic 1H NMR, 13C NMR, COSY, HMQC, and FT-IR techniques. The structure of both complexes was also confirmed by single crystal X-ray diffraction studies. The study of X-ray single crystal diffraction shows that the supramolecular aggregation of the complexes is stabilized via weak interactions as well as stacking interactions such as C-H···π and π···π. The cis-[Pt(L1-S,O)2 showed C–H···π and π···π stacking interactions, whereas only C–H···π stacking interaction was observed in cis-[Pt(L2-S,O)2]. In addition, the strong classical and non-classical intermolecular hydrogen bonds are not found in the prepared complexes. Therefore, it can be said that the C–H···π and π···π stacking interactions play an important role in the formation of supramolecular structures of the complexes.

High-temperature structural study of decagonal Al–Cu–Rh

2014 ◽  
Vol 70 (2) ◽  
pp. 306-314 ◽  
Author(s):  
Pawel Kuczera ◽  
Janusz Wolny ◽  
Walter Steurer
Keyword(s):  
High Temperature ◽  
Single Crystal ◽  
Structural Study ◽  
Structural Disorder ◽  
X Ray Diffraction ◽  
X Ray ◽  
Decagonal Phase ◽  
Comparative Structure ◽  
The Stability

The structure of decagonal Al–Cu–Rh has been studied as a function of temperature byin-situsingle-crystal X-ray diffraction in order to contribute to the discussion on energy or entropy stabilization of quasicrystals. The experiments were performed at 293, 1223, 1153, 1083 and 1013 K. A common subset of 1460 unique reflections was used for the comparative structure refinements at each temperature. A comparison of the high-temperature datasets suggests that the best quasiperiodic ordering should exist between 1083 and 1153 K. However, neither the refined structures nor the phasonic displacement parameter vary significantly with temperature. This indicates that the phasonic contribution to entropy does not seem to play a major role in the stability of this decagonal phase in contrast to other kinds of structural disorder, which suggests that, in this respect, this decagonal phase would be similar to other complex intermetallic high-temperature phases.

Luminescent Silver(I) and Copper(I) Systems Containing Pyridyl Phosphine Bridges

2009 ◽  
Vol 64 (11-12) ◽  
pp. 1525-1534 ◽  
Author(s):  
Olga Crespo ◽  
M. Concepción Gimeno ◽  
Antonio Laguna ◽  
Carmen Larraz
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Room Temperature ◽  
Silver Salt ◽  
Phosphine Ligands ◽  
X Ray Diffraction ◽  
X Ray ◽  
Molar Ratios ◽  
Pyridylphosphine Ligands

Luminescent silver(I) and copper(I) complexes containing pyridylphosphine ligands have been synthesized and structurally characterized by single crystal X-ray diffraction methods. The reaction of Ag(OTf) (OTf = trifluoromethanesulfonate) with 2-pyridyldiphenylphosphine in different molar ratios gives the species [Ag2(OTf)2(μ-PPh2py)2] (1), [Ag(PPh2py)2]OTf (2), [Ag(PPh2py)3]OTf (3), and [Ag2(PPh2py)3](OTf)2 (4) with several modes of coordination of the pyridylphosphine. The oxidation of the phosphine in compound 4 gave [Ag2(OTf)(μ-PPh2py)2(OPPh2py)]OTf (5) which has been structurally characterized. It shows two bridging phosphine ligands and one chelating OPPh2py ligand. The reactions of the silver salt with bis(2-pyridyl)phenylphosphine in different molar ratios affords the complex [Ag2(OTf)2(μ-PPhpy2)2] (6), while the corresponding reactions with [Cu(NCMe)4]PF6 lead to two different compounds, namely [Cu2(NCMe)2(μ-PPhpy2)2](PF6)2 (7) and [Cu2(PPhpy2)2(μ-PPhpy2)2](PF6)2 (8). All complexes exhibit luminescence in the solid state at room temperature and at 77 K

Undistorted linear Bi chains with hypervalent bonding in La3TiBi5 from single-crystal X-ray diffraction

2018 ◽  
Vol 74 (5) ◽  
pp. 618-622 ◽  
Author(s):  
Alexander Ovchinnikov ◽  
Svilen Bobev
Keyword(s):  
Electronic Structure ◽  
Single Crystal ◽  
Three Dimensional ◽  
Atomic Displacement ◽  
X Ray Diffraction ◽  
One Dimensional ◽  
X Ray ◽  
Orbital Mixing ◽  
The Stability ◽  
Structure Calculations

The crystal structure of the lanthanum titanium bismuthide La3TiBi5 (Pearson code hP18, Wyckoff sequence b d g2) has been established from single-crystal X-ray diffraction data and analyzed in detail using first-principles calculations. There are no anomalies pertaining to the atomic displacement parameter of the Ti site, previously reported based on a powder X-ray diffraction analysis of this compound. The anionic substructure contains columns of face-sharing TiBi6 octahedra and linear Bi chains. Due to a significant La(5d) and Bi(6p) orbital mixing, a perfectly one-dimensional character of the Bi chains is not realised, while a three-dimensional electronic structure is established instead. The latter fact explains the stability of the polyanionic pnictide units against Peierls distortions. The hypervalent bonding in the Bi chains is reflected in a rather long Bi—Bi distance of 3.2264 (4) Å and a typical pattern of bonding and antibonding interactions, as revealed by electronic structure calculations.

Crystal structure refinement of MnTe2, MnSe2, and MnS2: cation-anion and anion–anion bonding distances in pyrite-type structures

2019 ◽  
Vol 234 (6) ◽  
pp. 371-377 ◽  
Author(s):  
Makoto Tokuda ◽  
Akira Yoshiasa ◽  
Tsutomu Mashimo ◽  
Hiroshi Arima ◽  
Hidetomo Hongu ◽  
...  
Keyword(s):  
Single Crystal ◽  
Spin State ◽  
Structure Refinement ◽  
Mean Square Displacement ◽  
Structural Refinement ◽  
X Ray Diffraction ◽  
X Ray ◽  
Structural Differences ◽  
The Mean ◽  
The Stability

Abstract The stability of hauerite (MnS2) as compared to that of pyrite (FeS2) can be explained by the long Mn–S distance and departure from the typical pyrite-type structures. The structural differences of MnX2 compounds (X=S, Se, and Te) are the result of spin configurations that are different than those of other MX2 compounds; however, the arrangement of d-electrons and the size of the ions in MnX2 compounds do not clearly explain why Mn2+ in MnX2 does not exist as a low spin state. To investigate the structural differences of MnX2 compounds, we synthesized single-crystal MnTe2 and MnSe2 and performed single-crsytal X-ray diffraction experiments. The single-crystal X-ray diffraction experiments were conducted on MnTe2 [a=6.9513(1) Å, u-parameter=0.38554(2), space group Pa3̅, Z=4], MnSe2 [a=6.4275(2) Å, u-parameter=0.39358(2)], MnS2 [hauerite; a=6.1013(1) Å, u-parameter=0.40105(4), obtained from Osorezan, Aomori, Japan], and FeS2 [pyrite; a=5.4190(1) Å, u-parameter 0.38484(5), obtained from Kawarakoba, Nagasaki, Japan]. The X-ray intensity datasets of these compounds do not show any evidence of symmetry reduction. In MnS2, the S–S distance is 2.0915(8) Å, which is significantly shorter than that of FeS2 (2.1618(9) Å), and the mean square displacement of S (U11=0.00915(9) Å2) is smaller than that of Mn (U11=0.01137(9) Å2). The thermal vibration characteristics of MnX2 compounds are significantly different than those of FeS2. Based on structural refinement data, we discuss the low spin state of MnX2 compounds and the structural stability of pyrite-type structures.

Macrocyclic tetrakis-phosphines and their copper(I) complexes

2017 ◽  
Vol 89 (3) ◽  
pp. 331-339 ◽  
Author(s):  
Elvira I. Musina ◽  
Tatiana I. Wittmann ◽  
Alexey B. Dobrynin ◽  
Peter Lönnecke ◽  
Evamarie Hey-Hawkins ◽  
...  
Keyword(s):  
Single Crystal ◽  
Phosphine Ligands ◽  
X Ray Diffraction ◽  
Tetranuclear Complex ◽  
X Ray

AbstractA series of mono-, di- and tetranuclear copper(I) complexes with macrocyclic 14-, 16-, 18- and 20-membered tetrakis-phosphine ligands (P4N2) was obtained and fully characterized including single crystal X-ray diffraction. The 14-membered P4N2 macrocycles form very stable cationic mononuclear tetraphospha-coordinated copper(I) complexes, whereas their higher 16-, 18- and 20-membered homologues give neutral dinuclear [Cu2I2L] complexes under the same conditions. An unusual tetranuclear complex with two three- and two four-coordinated copper(I) atoms was obtained from 16-PMes4NCH2CH2Py-22 and copper(I) iodide. This is the first example of N-coordination of cyclic aminomethylphosphines towards “soft” copper(I).

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