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Synthesis, characterization, crystal structures, Hirshfeld surface analysis and theoretical calculations of some new bisphosphoramidate derivatives and novel binuclear triorganotin(IV) complexes with diphosphoryl ligand

Published on Jan 1, 2019in Journal of Organometallic Chemistry2.07
· DOI :10.1016/j.jorganchem.2018.10.012
Khodayar Gholivand19
Estimated H-index: 19
(TMU: Tarbiat Modares University),
Masoumeh Azadbakht1
Estimated H-index: 1
(TMU: Tarbiat Modares University)
+ 2 AuthorsCanan Kazak15
Estimated H-index: 15
(OMU: Ondokuz Mayıs University)
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Abstract
Abstract A series of new bisphosphoramidate and (thio)phosphoramidate derivatives with the general formula R 1 R 2 P(X)–Y–P(X)R 1 R 2 have been synthesized and characterized by IR and NMR spectroscopies ( L 1 – L 12 ). The crystal structure of compound 1,4-[(C 2 H 5 O) 2 P(S)(CH 2 ) 3 NH] 2 C 4 H 8 N 2 ( L 4 ) is also investigated by X-ray diffraction analysis. Two novel organotin(IV) complexes μ-{1,4-[(C 6 H 5 ) 2 P(O)(CH 2 ) 3 NH] 2 C 4 H 8 N 2 }[SnR 3 Cl] 2 , R 3 SnCl (R = phenyl/butyl), C 1 and C 2 , respectively, are prepared by the reaction of new diphosphoryl ligand L 1 and R 3 SnCl under different conditions. C 1 and C 2 are characterized by IR and NMR spectroscopies and X-ray crystallography diffraction analysis. X-ray analysis illustrates that both complexes have similar structures containing binuclear triorganotin(IV) skeletons and ligand coordinates in a bridging mode through two phosphoryl groups. Sn(IV) coordination geometries are distorted trigonal bipyramidal (TBP) for C 1, and C 2 structures contained binuclear arrangement with two SnPh 3 Cl/SnBu 3 Cl groups linked via the bridging diphosphoryl ligand. The organization of the crystal structures and the intermolecular interactions are discussed. Hirshfeld surfaces and two-dimensional fingerprint plots are used to study short intermolecular contacts in C 1 , C 2, and L 4 . Finally, the influence of chain length and the effects of various substituents on P=O and P=S bond strength in synthesized ligands ( L 1 – L 12 ) and optimized ligands ( L 13 – L 17 ) are theoretically investigated by NBO analysis to survey the character of mentioned bonds in these ligands. The AIM analysis is also used to determine the nature of the P=O bond in L 1 and also P=O and O⋯Sn 4+ bonds in C 1 and C 2 . Results show ionic character for O⋯Sn 4+ interaction in both complexes and mostly electrostatic character for P=O bond in the free ligand, but with a little shift to the covalent character after the complexation.
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  • Citations (1)
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References45
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Published on Jan 1, 2017in CrystEngComm3.38
Khodayar Gholivand19
Estimated H-index: 19
(TMU: Tarbiat Modares University),
Mahdieh Hosseini3
Estimated H-index: 3
(TMU: Tarbiat Modares University)
+ 1 AuthorsKaveh Farshadfar3
Estimated H-index: 3
(TMU: Tarbiat Modares University)
Herein, we report on the synthesis of a novel bisphosphoramidate compound (LOPhAn), (C6H5O)(C6H5NH)P(O)NC4H8N(O)P(OC6H5)(NHC6H5), with two polymorphic (I and III) and one methanol solvated pseudo-polymorphic (II.MeOH) structures in the solid state obtained by crystal growth from different solvents. Single crystal X-ray analysis revealed that Form (I) has one extended conformer of LOPhAn in the solid state, while Form (II) demonstrated one twisted conformer as well as the coexistence of solvent m...
Published on Dec 10, 2013in Journal of Coordination Chemistry1.69
Khodayar Gholivand19
Estimated H-index: 19
(TMU: Tarbiat Modares University),
Maryam Rajabi4
Estimated H-index: 4
(TMU: Tarbiat Modares University)
+ 2 AuthorsSedigheh Farshadian5
Estimated H-index: 5
(TMU: Tarbiat Modares University)
A new phosphoryl-containing ligand, N-isonicotinyl, N′,N′′-bis(hexamethylenyl) phosphoric triamide (1), was synthesized and characterized using IR, 1H, 13C, and 31P NMR and UV–vis spectroscopy. Reaction of 1 with MnCl2·4H2O led to the formation of Mn(II) complex with the formula {Mn[4-NC5H4C(O)NHP(O)(NC6H12)2]2Cl2}n (2). Crystal structures of 1 and 2 were determined by X-ray crystallography, which reveals that 2 is centrosymmetric with two phosphoryl oxygens, chloride and nitrogen in trans posit...
Published on Jan 1, 2012in Dalton Transactions4.05
Khodayar Gholivand19
Estimated H-index: 19
(TMU: Tarbiat Modares University),
Hamid Reza Mahzouni8
Estimated H-index: 8
(TMU: Tarbiat Modares University),
Mehdi D. Esrafili30
Estimated H-index: 30
(University of Maragheh)
A new family of isostructural early lanthanide(III) complexes (LnXPA) of the general formula Ln(XPA)2Cl3(solv)2, where Ln = La, Ce and Nd, XPA = (4-X-C6H4NH)P(O)(NC4H8O)2, X = H, F, Cl and Br, and solv = H2O and CH3OH, is introduced. X-ray crystallography shows that the replacement of the coordinated water by a methanol molecule may reduce the symmetry level of the unit cell from the orthorhombic crystal system and the space groupFdd2 to monoclinic and C2/c. DFT calculations, at B3LYP, PBE and B...
Published on Dec 10, 2011in Journal of Coordination Chemistry1.69
Khodayar Gholivand19
Estimated H-index: 19
(TMU: Tarbiat Modares University),
Rouhollah Yaghoubi3
Estimated H-index: 3
(TMU: Tarbiat Modares University)
+ 1 AuthorsZahra Hosseini5
Estimated H-index: 5
(TMU: Tarbiat Modares University)
Hydrothermal reaction of N-methyl-iminobis(methylenephosphonic acid), CH3N(CH2PO3H2)2, (H4L) with copper(II) acetate afforded a new layered Cu(II) amino diphosphonate, Cu3(H2O)2(HL)2 · 2H2O (1). Compound 1 was studied by IR spectroscopy, TGA/DTA data, and X-ray diffraction (XRD) techniques. The XRD patterns are the same for the hydrated and the dehydrated complexes. A single-crystal X-ray crystallographic determination reveals copper in two different coordination environments. Cu1 has a distorte...
Published on Jul 1, 2011in Bioorganic & Medicinal Chemistry Letters2.45
Longqin Hu24
Estimated H-index: 24
(RU: Rutgers University),
Xinghua Wu6
Estimated H-index: 6
(RU: Rutgers University)
+ 9 AuthorsPeter F. Searle30
Estimated H-index: 30
(University of Birmingham)
Abstract A series of nitrobenzyl phosphoramide mustards and their analogs was designed and synthesized to explore their structure–activity relationships as substrates of nitroreductases from Escherichia coli and trypanosomes and as potential antiproliferative and antiparasitic agents. The position of the nitro group on the phenyl ring was important with the 4-nitrobenzyl phosphoramide mustard ( 1 ) offering the best combination of enzyme activity and antiproliferative effect against both mammali...
Published on Aug 1, 2009in Bioorganic & Medicinal Chemistry Letters2.45
Christopher McGuigan35
Estimated H-index: 35
(Cardiff University),
Mary Rose Kelleher3
Estimated H-index: 3
(Cardiff University)
+ 9 AuthorsJoseph A. Martin6
Estimated H-index: 6
(Hoffmann-La Roche)
Abstract We report the design, synthesis and evaluation of a family of ca 50 phosphoramidate ProTides of the potent anti-HCV compound 4′-azidocytidine (R1479), with variation on the ester, amino acid and aryl moiety of the ProTide. Sub-μM inhibitors of HCV emerge. The compounds are all non-cytotoxic in the replicon assay. We herein report detailed SARs for each of the regions of the ProTide.
Published on Jun 1, 2009in Bioorganic & Medicinal Chemistry Letters2.45
Christopher McGuigan35
Estimated H-index: 35
(Cardiff University),
Felice Daverio6
Estimated H-index: 6
(Cardiff University)
+ 3 AuthorsDavid Bernard Smith11
Estimated H-index: 11
(Hoffmann-La Roche)
Novel phosphoramidate ProTides derived from 4′-azidoinosine have been prepared and evaluated in the replicon assay against hepatitis C Virus (HCV). The parent nucleoside analogue is inactive in this assay, while the ProTides are active at low μM levels in some cases. This is a rare example of an inosine nucleoside analogue with potent antiviral activity and further supports the notion of ProTides as a drug discovery motif.
Published on May 1, 2009in Bioorganic & Medicinal Chemistry Letters2.45
Yongying Jiang8
Estimated H-index: 8
(RU: Rutgers University),
Robert S. DiPaola45
Estimated H-index: 45
,
Longqin Hu24
Estimated H-index: 24
(RU: Rutgers University)
Abstract In an effort to develop proteolytically activated prodrugs of phosphoramide mustard by prostate-specific antigen (PSA), a series of tetrapeptide (Cbz-Ser-Ser-Phe-Tyr)-conjugated 4-aminocyclophosphamide (4-NH 2 -CPA) isomers were synthesized and evaluated as substrates of PSA. The cleavage of the conjugates by PSA were found to be stereoselective as only the two isomers with 4 R -configuration were efficiently cleaved by PSA. The cis - ( 2R , 4R ) - isomer was the best substrate of PSA w...
Published on May 1, 2009in Polyhedron2.28
Olesia V. Moroz10
Estimated H-index: 10
(KNU: Taras Shevchenko National University of Kyiv),
Victor A. Trush8
Estimated H-index: 8
(KNU: Taras Shevchenko National University of Kyiv)
+ 4 AuthorsVladimir M. Amirkhanov16
Estimated H-index: 16
(KNU: Taras Shevchenko National University of Kyiv)
Abstract The reaction of sodium dimethyl(phenylsulfonyl)amidophosphate Na L (H L = C 6 H 5 SO 2 NHP(O)(OCH 3 ) 2 ) with Cu(NO 3 ) 2 · 6H 2 O and o-bpe (1,2-bis(pyridine-2-yl)ethane) in appropriate ratios, afford the formation of 1D coordination polymer [Cu( L ) 2 · o-bpe ] n in good yield. The crystal structures of H L ( 1 ) and [Cu( L ) 2 · o-bpe ] n ( 2 ) are reported. In the crystal package the molecules of 1 are linked by intermolecular hydrogen bonds formed by the phosphoryl oxygen atoms wh...
Published on Jul 1, 2008in Bioorganic & Medicinal Chemistry Letters2.45
Yongying Jiang8
Estimated H-index: 8
(RU: Rutgers University),
Longqin Hu24
Estimated H-index: 24
(RU: Rutgers University)
Abstract N -(2,2-Dimethyl-2-(2-nitrophenyl)acetyl)-4-aminocyclophosphamide isomers (DMNA-NH-CPA, 4 ) were synthesized stereospecifically from Boc- l -Hse(OBn)-OH and the degradation of the corresponding reduced amine 5a was investigated by UV/vis spectroscopy and LC/MS. The rate of cyclization of 5a was found to increase with decreasing pH, with half-lives ranging from 3.2 to 54 min at pH 4–7.4, suggesting that the cyclization is catalyzed by the hydronium ions. LC/MS analysis of the degradation...
View next paperNovel organotin(IV) complexes of organophosphorus ligands: Synthesis, spectroscopic, structural study and DFT calculations