This document describes the synthesis and characterization of palladium(II) and platinum(II) complexes containing 1,1-bis(diphenylphosphino)ferrocene (dppf) and heterocyclic thionate ligands. Single crystal X-ray diffraction studies of two complexes, [Pt(Phozt)2(μ2-dppf)] and [Pd(bzoxt)2(μ2-dppf)], show that the ligands are coordinated in a monodentate fashion through the sulfur atom. The complexes were synthesized by reacting [MCl2(μ2-dppf)] (M = Pd, Pt) with two equivalents of potassium salts of heterocyclic th
Structural and Spectroscopical Studies for a Complex Macromolecule (hGH)IOSR Journals
Abstract: This paper tries to find the effect of the different environmental changes of ( pH, ionic strength, and temperature) on their tertiary structure of hGH by using UV sepctoscopy. We found that the hormone affected by chemical reagents change its conformation and folding. The present study is an attempt to discover what could happen to GH molecule when the biochemistry of body is changed. The results reveal that tryptophyl residues are inside the hormone, whereas tyrosyl residues are on the surface.
An efficient synthesis, characterization and antibacterial activity of novel ...iosrjce
IOSR Journal of Applied Chemistry (IOSR-JAC) is a double blind peer reviewed International Journal that provides rapid publication (within a month) of articles in all areas of applied chemistry and its applications. The journal welcomes publications of high quality papers on theoretical developments and practical applications in Chemical Science. Original research papers, state-of-the-art reviews, and high quality technical notes are invited for publications.
Simple Synthesis of Some Novel Polyfunctionally Derivatives of 2H-Coumarin-2-...IOSRJAC
Compound (2) was prepared from the reaction of ethyl-2-oxo-2H-coumarin-3-carboxylate (1) with ethylcyanoacetate in ethanol containing a catalytic amount of piperidine as catalyst. Compound (2) is the key intermediate for the synthesis of several series of new compounds such as ((pyrimidine, tetrazine, piperidine, oxazepine)-2H-coumarin-2-one derivatives by reaction with selected reagents such as urea, cyanoacetamide, cyanoacetohydrazide, orthoaminophenol and 5-aminotriazole.
Structural and Spectroscopical Studies for a Complex Macromolecule (hGH)IOSR Journals
Abstract: This paper tries to find the effect of the different environmental changes of ( pH, ionic strength, and temperature) on their tertiary structure of hGH by using UV sepctoscopy. We found that the hormone affected by chemical reagents change its conformation and folding. The present study is an attempt to discover what could happen to GH molecule when the biochemistry of body is changed. The results reveal that tryptophyl residues are inside the hormone, whereas tyrosyl residues are on the surface.
An efficient synthesis, characterization and antibacterial activity of novel ...iosrjce
IOSR Journal of Applied Chemistry (IOSR-JAC) is a double blind peer reviewed International Journal that provides rapid publication (within a month) of articles in all areas of applied chemistry and its applications. The journal welcomes publications of high quality papers on theoretical developments and practical applications in Chemical Science. Original research papers, state-of-the-art reviews, and high quality technical notes are invited for publications.
Simple Synthesis of Some Novel Polyfunctionally Derivatives of 2H-Coumarin-2-...IOSRJAC
Compound (2) was prepared from the reaction of ethyl-2-oxo-2H-coumarin-3-carboxylate (1) with ethylcyanoacetate in ethanol containing a catalytic amount of piperidine as catalyst. Compound (2) is the key intermediate for the synthesis of several series of new compounds such as ((pyrimidine, tetrazine, piperidine, oxazepine)-2H-coumarin-2-one derivatives by reaction with selected reagents such as urea, cyanoacetamide, cyanoacetohydrazide, orthoaminophenol and 5-aminotriazole.
Simple and Eco-friendly Synthesis of Glycosides bearing triazolo[3,4-b][1,3,4...IOSRJAC
There is a vast variety of naturally occurring glycosides which have marked pharmacological properties. These glycosides have widely diversed functional groups modifications which result in influencing pharmacological performance of corresponding glycosides. The 3,6-disubstituted-s-triazolo[3,4- b][1,3,4]thiadiazoles were glucosidated with 2,3,4,6tetra-o-acetyl α D glulopryanosyl bromide using simple methodologies. The compounds obtained in good yield in a 80-90 minutes.
Complete NMR Assignment of MogrosidesII A2, II E andIII A1Isolated from Luo H...iosrphr_editor
NMR analysis allowed complete assignments of three known mogrol glycosides, Mogroside IIA2 (1),
II E (2)and IIIA1 (3), isolated from the extracts of Luo Han Guo. Herein, complete 1H and 13C NMR
assignmentsof all threemogrosidesare described based on NMR experiments (1H NMR, 13C NMR, COSY,
HSQC-DEPT, HMBC, NOESY and 1DTOCSY) and mass spectral data.
Synthesis of Novel Piperidine Compounds As Anticholinesterase Agentsinventionjournals
Donepezil is a piperidine based agent that is used for treatment of Alzheimer’s diseases. This agent acts as acetylcholine esterase inhibitor and therefore, synthesis of piperidine compounds to evaluate anticholinesterase activity is very popular field in medicinal chemistry. Thus, in this study some novel piperidine derivatives were synthesized in order to observe their probable anticholinesterase effects. Structures of obtained compounds were confirmed by IR, NMR and Mass spectroscopic methods. Anticholinesterase activity of the synthesized compounds were tested by using Ellman’s method. Some of the compounds in the series indicated good enzyme inhibitory activity
Synthesis, characterization and antimicrobial evaluation of novel diethyl (2-...iosrphr_editor
The IOSR Journal of Pharmacy (IOSRPHR) is an open access online & offline peer reviewed international journal, which publishes innovative research papers, reviews, mini-reviews, short communications and notes dealing with Pharmaceutical Sciences( Pharmaceutical Technology, Pharmaceutics, Biopharmaceutics, Pharmacokinetics, Pharmaceutical/Medicinal Chemistry, Computational Chemistry and Molecular Drug Design, Pharmacognosy & Phytochemistry, Pharmacology, Pharmaceutical Analysis, Pharmacy Practice, Clinical and Hospital Pharmacy, Cell Biology, Genomics and Proteomics, Pharmacogenomics, Bioinformatics and Biotechnology of Pharmaceutical Interest........more details on Aim & Scope).
ER Publication,
IJETR, IJMCTR,
Journals,
International Journals,
High Impact Journals,
Monthly Journal,
Good quality Journals,
Research,
Research Papers,
Research Article,
Free Journals, Open access Journals,
erpublication.org,
Engineering Journal,
Science Journals,
The IOSR Journal of Pharmacy (IOSRPHR) is an open access online & offline peer reviewed international journal, which publishes innovative research papers, reviews, mini-reviews, short communications and notes dealing with Pharmaceutical Sciences( Pharmaceutical Technology, Pharmaceutics, Biopharmaceutics, Pharmacokinetics, Pharmaceutical/Medicinal Chemistry, Computational Chemistry and Molecular Drug Design, Pharmacognosy & Phytochemistry, Pharmacology, Pharmaceutical Analysis, Pharmacy Practice, Clinical and Hospital Pharmacy, Cell Biology, Genomics and Proteomics, Pharmacogenomics, Bioinformatics and Biotechnology of Pharmaceutical Interest........more details on Aim & Scope).
All manuscripts are subject to rapid peer review. Those of high quality (not previously published and not under consideration for publication in another journal) will be published without delay.
Simple and Eco-friendly Synthesis of Glycosides bearing triazolo[3,4-b][1,3,4...IOSRJAC
There is a vast variety of naturally occurring glycosides which have marked pharmacological properties. These glycosides have widely diversed functional groups modifications which result in influencing pharmacological performance of corresponding glycosides. The 3,6-disubstituted-s-triazolo[3,4- b][1,3,4]thiadiazoles were glucosidated with 2,3,4,6tetra-o-acetyl α D glulopryanosyl bromide using simple methodologies. The compounds obtained in good yield in a 80-90 minutes.
Complete NMR Assignment of MogrosidesII A2, II E andIII A1Isolated from Luo H...iosrphr_editor
NMR analysis allowed complete assignments of three known mogrol glycosides, Mogroside IIA2 (1),
II E (2)and IIIA1 (3), isolated from the extracts of Luo Han Guo. Herein, complete 1H and 13C NMR
assignmentsof all threemogrosidesare described based on NMR experiments (1H NMR, 13C NMR, COSY,
HSQC-DEPT, HMBC, NOESY and 1DTOCSY) and mass spectral data.
Synthesis of Novel Piperidine Compounds As Anticholinesterase Agentsinventionjournals
Donepezil is a piperidine based agent that is used for treatment of Alzheimer’s diseases. This agent acts as acetylcholine esterase inhibitor and therefore, synthesis of piperidine compounds to evaluate anticholinesterase activity is very popular field in medicinal chemistry. Thus, in this study some novel piperidine derivatives were synthesized in order to observe their probable anticholinesterase effects. Structures of obtained compounds were confirmed by IR, NMR and Mass spectroscopic methods. Anticholinesterase activity of the synthesized compounds were tested by using Ellman’s method. Some of the compounds in the series indicated good enzyme inhibitory activity
Synthesis, characterization and antimicrobial evaluation of novel diethyl (2-...iosrphr_editor
The IOSR Journal of Pharmacy (IOSRPHR) is an open access online & offline peer reviewed international journal, which publishes innovative research papers, reviews, mini-reviews, short communications and notes dealing with Pharmaceutical Sciences( Pharmaceutical Technology, Pharmaceutics, Biopharmaceutics, Pharmacokinetics, Pharmaceutical/Medicinal Chemistry, Computational Chemistry and Molecular Drug Design, Pharmacognosy & Phytochemistry, Pharmacology, Pharmaceutical Analysis, Pharmacy Practice, Clinical and Hospital Pharmacy, Cell Biology, Genomics and Proteomics, Pharmacogenomics, Bioinformatics and Biotechnology of Pharmaceutical Interest........more details on Aim & Scope).
ER Publication,
IJETR, IJMCTR,
Journals,
International Journals,
High Impact Journals,
Monthly Journal,
Good quality Journals,
Research,
Research Papers,
Research Article,
Free Journals, Open access Journals,
erpublication.org,
Engineering Journal,
Science Journals,
The IOSR Journal of Pharmacy (IOSRPHR) is an open access online & offline peer reviewed international journal, which publishes innovative research papers, reviews, mini-reviews, short communications and notes dealing with Pharmaceutical Sciences( Pharmaceutical Technology, Pharmaceutics, Biopharmaceutics, Pharmacokinetics, Pharmaceutical/Medicinal Chemistry, Computational Chemistry and Molecular Drug Design, Pharmacognosy & Phytochemistry, Pharmacology, Pharmaceutical Analysis, Pharmacy Practice, Clinical and Hospital Pharmacy, Cell Biology, Genomics and Proteomics, Pharmacogenomics, Bioinformatics and Biotechnology of Pharmaceutical Interest........more details on Aim & Scope).
All manuscripts are subject to rapid peer review. Those of high quality (not previously published and not under consideration for publication in another journal) will be published without delay.
Based on my book of the same title, Leveraging Your Leadership Style (LYLS) will equip you to be more effective in your leadership journey. Understand your personal style, the style of other team members, how you can be a dynamic leader in your team, and how your organization can achieve its goals through effective use of your style and the styles of others
Synthesis of substituted 1, 2, 4-triazole derivatives by Microwave irradiationIOSR Journals
Various substituted Triazole-Thiol containing different functional group have been synthesized by microwave method. The title product 1-[(3H-indol-2-ylamino) methyl]-4-phenyl-4, 5-dihydro-1H-1, 2, 4-triazole-3-thiol is synthesized by using amino benzothiazole. The final structures have been established on the basis of their chemical analysis and spectral data. All micro-wave synthesized compounds results into good yield as compared to conventional method of which fluoro substituted compound shows maximum yield.
Synthesis And Antibacterial Activity Of 3-[(3-Phenyl-5-Thioxo-1, 5-Dihydro-4h...inventionjournals
A series of 3-[(3-phenyl-5-thioxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)imino]-1,3-dihydro-2Hindole-2-one derivatives were synthesised through the nucleophilic substitution at carbonyl carbon of Isatin. Structure of synthesized compounds were elucidated by using IR, 1H NMR & 13C NMR spectrometry. Synthesised compounds showed significant antibacterial activity against E.coli (ATCC 35218), S.aureus (ATCC 25323), E.faecalis (Clinical isolate), K. Pneumonia, P. aeruginosa (ATCC 27893) using agar well diffusion method.
An Efficient Synthetic Approach Towards 4-Cyano-3-(Methylthio)-5-Oxo-2H-Pyraz...inventionjournals
ABSTRACT: Synthesis of novel heterocyclic 4-cyano -3-(methylthio)-5-oxo-2H-pyrazole-1(5H)- carbothioamide (3) was prepared by condensing ethyl-2-cyano-3,3-bis (methylthio)acrylate (1) with thiosemicarbazide (2) in DMF and catalytic amount of potassium carbonate. Compound (3) has methylthio group at third position, which is replaced by different nucleophiles such as substituted anilines| phenols| hetryl amines| compounds containing active methylene group to afford 3-substituted derivatives of compound (3). All the newly synthesized compounds were screened for their antimicrobial activity.
SYNTHESIS AND CHARACTERIZATION OF SOME TRANSITION METAL COMPLEXES WITH A NEW ...EDITOR IJCRCPS
A new monodentate phosphorus yield Ph3P=CHC(O)C6H4-m-Br (L),was synthesized and characterized with elemental analysis as
well as various spectroscopic techniques. The reactions of the title ylide with mercury(II) halides in equimolar ratios using dry
methanol as solvent have yielded [L.HgX2]2 (X= Cl (1), Br (2), I (3)). The reaction of 1 equiv. this ylide with Cd(NO3)2.4H2O in the
same solvent give a polynuclear complex [Cd (L)(NO3)(μ-NO3)]n (4), followed by treatment with 2 equiv. AgNO3 and AgOTf led to
monomeric chelate complexes 5 and 6, respectively. Characterization of the obtained compounds was also performed by
elemental analysis, IR, 1H, 31P and 13C NMR. All DMSO-solved synthesized compounds were subjected to biological evaluation for
their antibacterial against 6 Gram positive and negative bacteria effects by disc diffusion method. Results showed antibacterial
activity for studied metal complexes and suggested their possible application as antibacterial agents.
Keywords: Phosphorus yields, mercury(II) complexes, silver(I) complexes, cadmium(II) complexes, antibacterial activity.
Four new trinuclear Fe(III) complexes involving tetradenta Schiff bases N,N1-bis(salicylidene) ethylenediamine-
(salenH2) or bis(salicylidene)-o-phenylenediamine-(salophH2) with 2,4,6-tris(2,5-dicarboxyphenylimino-4-formylphenoxy)-
1,3,5-triazine (DCPI-TRIPOD) or 2,4,6-tris(4-carboxyphenylimino-4¢-formylphenoxy)-1,3,5-triazine
(CPI-TRIPOD) have been synthesized and characterized by means of elemental analysis carrying out 1H-n.m.r., i.r.
spectroscopy, thermal analyses and magnetic susceptibility measurements. The complexes can also be characterized
as high-spin distorted octahedral FeIII bridged by carboxylic acids. The tricarboxylic acids play a role as bridges for
weak antiferromagnetic intramolecular exchange.
Synthesis, Physicochemical Characterization and Structure Determination of So...IOSR Journals
Some novel nickel(II) complexes with the ligand (z)-4-((2-hydroxy-3-
methoxyphenyl)diazenyl)-1,5-dimethyl-2-phenyl-1H-pyrazol-3-(2H)-one,GAAP,guiacolazoantipyrine, L
having molecular formulae [Ni(L)2X2] and [Ni(L)2(NCS)Cl] where X = Cl-, Br-, NO3
- were synthesized and
characterized. The elemental analysis, Spectral (IR, UV-Visible, EPR, FAB – mass) studies and thermo
gravimetric analysis reveals that the Ni(II) is six coordinated in its complexes. A rhombic symmetry can be
tentatively proposed for the complexes. The magnetic susceptibility measurements show that the complexes are
paramagnetic in nature. The powder XRD study shows its anisotropic nature
METALLO - BIOACTIVE COMPOUNDS AS POTENTIAL NOVEL ANTICANCER THERAPYijac123
Mono and bi-organometallic complexes of Cu(II), Ni(II), Mn(II), Zn(II) and Ag(I) complexes with
oxaloamide ligand has much potential as therapeutic and diagnostic agents. The ligand allows the
thermodynamic and kinetic reactivity of the metal ion to be controlled and also provide a scaffold for
functionalization. Specific examples involving the design of metal complexes as anticancer agents are
discussed. These complexes have been synthesized and characterized by (1H-NMR, mass, IR, UV-VIS,
ESR) spectra, magnetic moments and conductance measurements, elemental and thermal analyses. Molar
conductances in DMF solution indicates that, the complexes are non-electrolytes. The ESR spectra of solid
Cu(II) complexes (2-5) show an axial type indicating a d(X2-y2) ground state with a significant covalent
bond character. However, Mn(II) complex(9), shows an isotropic type indicating an octahedral geometry.
Cytotoxic evolution IC50 of the ligand and its complexes have been carried out. Cu(II) Complexes show
enhanced activity in comparison to the parent ligand or standard drug. Copper is enriched in various
human cancer tissues and is a co-factor essential for tumor angiogenesis processes. However, the use of
copper binding ligand to target tumor, copper could provide a novel strategy for cancer selective
treatment.
Photo-oxygenation of trans anethole (1), the main constituent of anise essential oil, using
tetraphenylporphyrine (TPP) as a singlet oxygen sensitizer in chloroform gave 4-methoxybenzaldehyde (p-anisaldhyde)
(2), 2-(4-methoxyphenyl)propan-2-ol (3) as well as erythro and threo 1-(4-methoxyphenyl)propane-1,2-diol (4a, 4b).
The structures of the photo-oxygenation products were elucidated by spectral means
Photo-oxygenation of trans anethole (1), the main constituent of anise essential oil, using tetraphenylporphyrine (TPP) as a singlet oxygen sensitizer in chloroform gave 4-methoxybenzaldehyde (p-anisaldhyde) (2), 2-(4-methoxyphenyl)propan-2-ol (3) as well as erythro and threo 1-(4-methoxyphenyl)propane-1,2-diol (4a, 4b). The structures of the photo-oxygenation products were elucidated by spectral means.
Synthesis, Characterization, and Antibacterial Activity of Some Novel 5-Chlor...IJERA Editor
The development of potential antibacterial requires the synthesis of a new series of 5- Chloroisatin derivatives incorporating various aromatic aldehydes in the case 1,3-Dipolar Cycloaddition including Nitrile oxide, as well as the cycloaddition Alcyne-Azide Catalytic with Copper. The charcterization of the structure of the synthesized compounds was confirmed by means of their IR, 1H-NMR and 13C-NMR spectral data. In addition, the antibacterial properties in vitro were tested against certain microorganisms using the disk diffusion technique. A majority of compounds show better activity against several of the microorganisms.
A series of novel 5-[2-(4-fluorobenzyl)-6-aryl-imidazo[2,1-b][1,3,4]thiadiazol-5-ylmethylene] thiazolidine-2,4-dione derivatives (4a-d) were synthesized. These final compounds (4a-d) were synthesized by Knoevenagel condensation of 2-(4-fluorobenzyl)-6-arylimidazo[2,1-b][1,3,4]thiadiazole-5-carbaldehydes (3a-d) with thiazolidine-2,4-dione. All the newly synthesized compounds were screened for their invivo hypoglycemic and hypolipidemic activity in male Wister rats. The Structures of all the newly synthesized compounds were established by analytical and spectral data.
ANTIMICROBIAL AND ANTIFUNGAL OF SOME NEW SEMISYNTHETIC TERPENOID DERIVATIVES ...Jing Zang
The synthesis of a series of euphorbol derivatives is described, starting from euphorbol isolated from fresh latex of Euphorbia resinifera Berg. Their structures have been established on the basis of spectral data. All compounds were evaluated for antibacterial activities against Escherichia coli and Staphyloccus aureus strains and antifungal activity against Candida albicans and Aspergillus niger strains by using serial dilution method. `
1. Heteroleptic palladium(II) and platinum(II) complexes of
1,1-bis(diphenylphosphino)ferrocene (dppf) and heterocyclic thionates: Crystal
structures of [Pt(Phozt)2(j2
-dppf)] (PhoztH = 5-phenyl-1,3,4-oxadiazole-2-thione)
and [Pd(bzoxt)2(j2
-dppf)] (bzoxtH = benz-1,3-oxazoline-2-thione)
Subhi A. Al-Jibori a,⇑
, Thaaer F. Khaleel a
, Shihab A.O. Ahmed a
, Lamaan J. Al-Hayaly b
, Kurt Merzweiler c
,
Christoph Wagner c
, Graeme Hogarth d,⇑
a
Department of Chemistry, College of Science, University of Tikrit, Tikrit, Iraq
b
Department of Chemistry, College of Pharmacy, Hawler University of Medicine, Erbil, Iraq
c
Institut fur Anorganische Chemie, Martin-Luther-Universität, Halle-Wittenberg, Kurt-Mothes-Str. 2, D-06120 Halle, Germany
d
Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, UK
a r t i c l e i n f o
Article history:
Received 31 December 2011
Accepted 11 April 2012
Available online 3 May 2012
Keywords:
Palladium
Platinum
1,1-Bis(diphenylphosphino)ferrocene
Complexes
X-ray studies
a b s t r a c t
Treatment of [MCl2(j2
-dppf)] (M = Pd or Pt) with two equivalents of potassium heterocyclic thionate
salts (KL) affords mixed ligand complexes [ML2(j2
-dppf)] [L = 5-phenyl-1,3,4-oxadiazole-2-thionate
(Phozt), 4,5-diphenyl-1,2,4-triazole-3-thionate (Ph2tzt), benz-1,3-thiazoline-2-thionate (bztzt) and
benz-1,3-oxazoline-2-thionate (bzoxt)]. X-ray structures of two examples, [Pt(Phozt)2(j2
-dppf)] and
[Pd(bzoxt)2(j2
-dppf)], show that the ligands are coordinated in a monodentate fashion via the sulfur
atom.
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
The coordination chemistry of heterocyclic thiones and thio-
nates is rich and varied with some examples having important
chemical and biological properties [1–6]. Thionates can exist in
two tautomeric forms which enables them to behave in an ambid-
entate fashion binding through either the sulfur (thiolate) or
nitrogen (thione) atom, while in some cases they can act as chelate
or bridging ligands upon binding of both of these atoms. These tau-
tomers are shown (Chart 1) for the specific ligands used in this
study which is part of our systematic investigation of the coordina-
tion chemistry of thioamide ligands [7–13]. Thus, we have
previously shown that complexes of the type [ML2(j2
-Ph2P(CH2)n
PPh2)] with mercapto-1,3-azole ligands, benz-1,3-thiazoline-2-
thionate (X = S, bztzt) and benz-1,3-oxazoline-2-thionate (X = O,
bzozt) exist as a mixture of isomers resulting from either the
N- or S-coordination of the ligands [13]. Herein we report the
synthesis and characterization of palladium(II) and platinum(II)
complexes of heterocyclic thionates containing the flexible diphos-
phine, 1,1-bis(diphenylphosphino)ferrocene (dppf) [14–20]. Some
related examples of platinum(II) with simple organic thiolates
and dppf have been recently reported [21,22].
2. Experimental
2.1. General
1
H and 13
C NMR spectra were recorded on Varian Unity 500 and
Gemini 2000 spectrometers, respectively, with CDCl3 as solvent
and internal reference. 31
P NMR spectra were recorded on a Gemini
2000 spectrometer with CDCl3 as solvent and H3PO4 (85%) as exter-
nal reference. The NMR spectra were measured at the Institut fur
Anorganische Chemie, Martin-Luther-Universität, Halle-Witten-
berg, Germany. IR spectra were recorded on a Shimadzu FT-IR
8400 spectrophotometer in the 200–4000 cmÀ1
range using CsI
discs. Elemental analyses were carried out on a CHN analyzer type
1106 (Carlo-Erba). Melting points were measured on electrother-
mal 9100 melting point apparatus and were uncorrected. K2[PtCl4],
1,1-bis(diphenylphosphino)ferrocene (dppf) benz-1,3-oxazoline-2-
thione, benz-1,3-thiazoline-2-thione were commercial products
and were used as supplied. The compounds 4,5-diphenyl-1,2,4-tri-
azole-3-thione [23], 5-phenyl-1,3,4-oxadiazole-2-thione [24],
trans-[PdCl2(DMSO)2], cis-[PdCl2(DMSO)2] [25], [PdCl2(j2
-dppf)]
0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.04.007
⇑ Corresponding authors.
E-mail address: g.hogarth@ucl.ac.uk (G. Hogarth).
Polyhedron 41 (2012) 20–24
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
2. and [PtCl2(j2
-dppf)] [20] were prepared by literature methods. The
potassium salts of all ligands used in this work were prepared by
mixing equimolar quantities of KOH and the ligand in EtOH. The
mixture was stirred at room temperature for 1 h. Solvent was then
evaporated on steam bath, and the resulting solid was dried under
vacuum.
2.2. Preparation of complexes
All the complexes were prepared and isolated by the following
general method. A solution of the appropriate potassium salt of the
ligand in a minimum amount of EtOH was added to a solution of
[MCl2(j2
-dppf)] (M = Pd or Pt) in a minimum a mount of CHCl3
in a mole ratio ligand to metal 2:1. The resulting solution was
boiled on steam bath for ca. 10 min. Solvent was then left to evap-
orate at room temperature. The resulting solid washed with water,
cold EtOH and dried under vacuum. Crystals of 2.EtOH and 6 suit-
able for single-crystal diffraction analysis were grown at 25 °C by
slow evaporation of chloroform–ethanol solutions.
Complex 1: Orange solid, 86%. Anal. Calc. for C50H38Fe-
N4O2P2PdS2: C, 58.9; H, 4.2; N, 5.3. Found: C, 59.0; H, 4.2; N,
5.5%. IR (KBr): 3470m, 3056m, 2925w, 1554m, 1305w, 1070m,
995m, 748s, 438m, 400w cmÀ1
. 1
H NMR (CDCl3): d 7.90–7.30 (m,
30H, Ph), 4.39 (m, 4H, Cp), 4.38 (m, 4H, Cp). 13
C{1
H} NMR (CDCl3):
171.4, 163.6, 134.8, 131.7, 131.5, 127.9, 124.8, 76.3, 74.0, 73.4 ppm.
31
P{1
H} NMR (CDCl3): d 31.7. Melting point: 210–213 °C.
Complex 2: Yellow solid, 79%. Anal. Calc. for C50H38Fe-
N4O2P2PtS2: C, 54.4; H, 3.5; N, 5.1. Found: C, 54.2; H, 3.4; N, 5.0%.
IR (KBr): 3057m, 2925w, 1554m, 1307m, 1070m, 995m, 755s,
441m, 400w cmÀ1
. 1
H NMR (CDCl3): d 7.87–7.30 (m, 30H, Ph),
4.36 (m, 8H, Cp). 13
C{1
H} NMR (CDCl3): 171.4, 163.6, 134.9,
131.0, 130.7, 127.8, 124.8, 76.1, 73.3 ppm. 31
P{1
H} NMR (CDCl3):
d 18.4 (JPt–P 3298 Hz). Melting point: 247–250 °C.
Complex 3: Orange solid, 76%. Anal. Calc. for C50H38FeN6P2PdS2:
C, 63.9; H, 4.2; N, 7.2. Found: C, 64.1; H, 4.4; N, 7.5%. IR (KBr):
3058m, 2925w, 1596m, 1255w, 1065m, 1033m, 767s, 439m,
400w cmÀ1
. 1
H NMR (CDCl3): d 7.97–6.80 (m, 40H, Ph), 4.43 (m,
4H, Cp), 4.31 (m, 4H, Cp). 13
C{1
H} NMR (CDCl3): 152.3, 135.1,
132.3, 130.5, 127.8, 76.0, 72.9 ppm. 31
P{1
H} NMR (CDCl3): d 29.6.
Melting point: 203–205 °C.
Complex 4: Red-brown solid, 88%. Anal. Calc. for C46H36FeN2P2
PdS4: C, 58.0; H, 3.7; N, 2.8. Found: C, 58.1; H, 3.8; N, 2.6%. IR
(KBr): 3057m, 2925w, 1587m, 1238m, 1097m, 1030m, 750s,
438m, 380w cmÀ1
. 1
H NMR (CDCl3): d 7.97–7.00 (m, 28H, Ph),
4.42 (m, 4H, Cp), 4.35 (m, 4H, Cp). 13
C{1
H} NMR (CDCl3): 176.5,
153.8, 137.3, 134.7, 132.1, 130.7, 127.7, 124.5, 121.9, 119.8,
119.0, 76.0, 74.8, 73.2 ppm. 31
P{1
H} NMR (CDCl3): d 27.5. Melting
point: 177–180 °C.
Complex 5: Yellow solid, 73%. Anal.Calc. for C46H36FeN2P2PtS4: C,
53.2; H, 3.4; N, 2.6. Found: C, 53.5; H, 3.2; N, 2.7%. IR (KBr): 3057m,
2925w, 1585m, 1240m, 1097m, 1031m, 752s, 437m, 380w cmÀ1
.
1
H NMR (CDCl3): d 7.85–6.95 (m, 28H, Ph), 4.30 (m, 8H, Cp).
13
C{1
H} NMR (CDCl3): 134.6, 134.0, 131.3, 130.7, 127.6, 124.3,
121.8, 119.6, 75.8, 73.2 ppm. 31
P{1
H} NMR (CDCl3): d 16.5 (JPt–P
3264 Hz). Melting point: 240–243 °C.
Complex 6: Red-brown solid, 91%. Anal. Calc. for
C46H36FeN2P2PdS2O2: C, 60.0; H, 3.8; N, 2.9. Found: C, 60.1; H,
3.9; N, 2.0%. IR (KBr): 3055m, 2925w, 1604m, 1244m, 1081m,
1037m, 748s, 433m, 380w cmÀ1
. 1
H NMR (CDCl3): d 7.98–7.10
(m, 28H, Ph), 4.44 (m, 4H, Cp), 4.37 (m, 4H, Cp). 13
C{1
H} NMR
(CDCl3): 151.6, 134.7, 131.3, 130.8, 122.5, 121.3, 115.6, 113.9,
108.4, 76.0, 73.2 ppm. 31
P{1
H} NMR (CDCl3): d 28.5. Melting point:
186–188 °C.
2.3. X-ray crystallography
Yellow crystals of 2 and red-brown crystals of 6 suitable for X-
ray crystallographic measurements were obtained by slow evapo-
ration of chloroform/ethanol (ca. 50:50) solutions of the respective
complex. Table 1 gives the crystallographic data and collection
parameters. Intensity data were collected on a STOE-IPDS diffrac-
tometer with Mo Ka radiation (k = 0.7103 Å, graphite monochro-
mator). Absorption corrections were made using the IPDS
software package [26]. All structures were solved by direct meth-
ods with SHELX-97 [27] and refined using full-matrix least-square
routines against F2
with SHELXL-97 [28]. Non-hydrogen atoms were
refined with anisotropic displacement parameters. Hydrogen
atoms were included in the models by calculating the positions
(riding model) and refined with calculated isotropic displacement
parameters. Illustrations were generated using DIAMOND 3.0 soft-
ware [29].
NN
E
S Ph
NN
E
S Ph
thiolate thione
X
N
X
N
SS
E = O, Phozt; E = NPh, Ph2tzt
X = S, bztzt; X = O, bzozt
Chart 1.
Table 1
Crystallographic and data collection parameters for complexes 2 and 6.
Complex 2.EtOH 6
Empirical formula C52H44FeN4O3P2PtS2 C48H36FeN2O2P2PdS2
Formula weight 1149.91 961.10
Crystal system triclinic orthorhombic
T (K) 223(2) 223(2)
Space group P1 Pna21
Z 2 4
a (Å) 9.4541(9) 23.5022(14)
b (Å) 15.223(2) 18.4617(16)
c (Å) 18.236(1) 9.8761(6)
a (°) 76.71(1) 90
b (°) 78.13(1) 90
c (°) 72.49(1) 90
V (Å3
) 2409.3(4) 4285.1(5)
q (g cmÀ3
) 1.585 1.490
l(Mo Ka) (mmÀ1
) 3.401 0.966
F(000) 1148 1952
Scan range (°) 1.99 25.84 2.05 h 25.88
Reciprocal lattice segments h,
k, l
À11 ? 11 À28 ? 28
À18 ? 18 À22 ? 22
À22 ? 22 À12 ? 11
Reflections collected 18742 33063
Reflections independent 8655 8155
Rint 0.0428 0.0502
Data/restraints/parameters 8655/0/587 8155/1/523
Goodness-of-fit on F2
0.972 0.985
R1, wR2 [I 2r(I)] 0.0305, 0.0645 0.0276, 0.0595
R1, wR2 (all data) 0.0496, 0.0778 0.0356, 0.0617
Largest difference in peak and
hole (e ÅÀ3
)
1.28 and À1.39 1.052 and À0.250
Absolute structure factor À0.015(14)
CCDC No. 767746 767747
S.A. Al-Jibori et al. / Polyhedron 41 (2012) 20–24 21
3. 3. Results and discussion
We have developed a three step synthesis of group 10 diphos-
phine–thionate complexes [ML2(j2
-diphosphine)] complexes
[8–13]. This involves treatment of thiones LH (LH = Phozt and
Ph2tzt) with palladium(II) or platinum(II) precursors including
Na2PdCl4, trans-[PdCl2(DMSO)2], K2PtCl4 or cis-[PtCl2(DMSO)2] to
give complexes of the type [MCl2(LH)2] (M = Pd or Pt). These can
then be converted to [ML2] by treatment with base, which in turn
react with diphosphines Ph2P(CH2)nPPh2 (n = 1–4) to give [ML2(j2
-
diphosphine)] in which the thionate anion binds to the metal
center in either the thiolate or thione form (Chart 1). Attempts to
prepare [ML2(j2
-dppf)] complexes via this method were only par-
tially successful leading to mixtures of products. While the desired
complexes 1–3 were generated (as confirmed by 1
H NMR spectros-
copy) we were unable to isolate pure products. The nature of the
secondary species is not clear but they possibly result from the
dppf ligand acting in a bridging rather than a chelating capacity
since it is well-known that dppf is a highly flexible diphosphine
[19]. We consequently sought another synthetic route to the de-
sired products and in contrast to the first route, treatment of
[MCl2(j2
-dppf)] (M = Pd, Pt) with two equivalents of the potassium
salt of 5-phenyl-1,3,4-oxadiazole-2-thionate (KPhozt) [24] in a
CHCl3/EtOH mixture cleanly afforded [M(Phozt)2(j2
-dppf)] (1–2)
after work-up as orange (M = Pd) and yellow (M = Pt) solids in
86% and 79% yield, respectively. A similar reaction between potas-
sium 4,5-diphenyl-1,2,4-triazole-3-thionate (KPh2tzt) [30] and
[PdCl2(j2
-dppf)] gave [Pd(Ph2tzt)2(j2
-dppf)] (3) as an orange solid
in 76% yield (Scheme 1).
Characterization was relatively straight-forward on the basis of
spectroscopic and analytical data. 1
H NMR spectra were as ex-
pected, each displaying multiplets between d 6.80–7.98 assigned
to the aromatic protons and either one or two broad signals be-
tween d 4.31–4.44 due to the protons of the cyclopentadienyl
ligands. The broadness of these later signals is attributed to the
well-known fluxionality of the dppf ligand [19,31]. In the 31
P{1
H}
NMR spectrum each shows a single phosphorus resonance indicat-
ing that both of the chlorides had been replaced and all exist in a
single isomeric form. The relatively small phosphorus–platinum
coupling constant for [Pt(Phozt)2(j2
-dppf)] (2) of 3298 Hz, respec-
tively, as compared to [PtCl2(j2
-dppf)] (JPt–P 3761.5 Hz) [20]
suggests the ligands bind through the sulfur atom, that is in a thio-
late fashion [32]. For comparison the phosphorus–platinum cou-
pling constant in the closely related complex [Pt(SPh)2(j2
-dppf)]
is 3016 Hz [21]. In order to confirm this, an X-ray crystal structure
was carried out on 2 the results of which are shown in Fig. 1. There
is also a molecule of ethanol in the asymmetric unit but there are
no significant intermolecular interactions and this will not be
considered further. Compound 2 consists of the expected PtS2P2
square-planar array as is seen in related complexes [21,32,33].
The dppf ligand subtends a bite-angle of 98.08(5)° and the ferro-
cene backbone is twisted out of the PtS2P2 plane with one cyclo-
pentadienyl ligand lying above and the second below. The key
feature is the binding of the thionate groups through sulfur. The
adoption of the thiolate resonance form is clearly seen from the
metal–sulfur distances (Pt–Sav. 2.388(2) Å) which are similar to
those found in other platinum thiolate and dithiolate complexes
[21,32,33] and the carbon–nitrogen bond lengths within the het-
erocyclic ring (C–Nav 1.31(1) Å) which are indicative of double
bond character. The two thiolate ligands lie relatively close to
one another [S(1)–Pt–S(2) 85.25(4)°] and in order to reduce steric
strain between them, substituents lie on opposite sides of the
PtS2P2 plane (anti-conformation). The bond angles at sulfur of
99.8(2)° and 99.9(2)° are significantly smaller than those seen in
[Pt(SPh)2(j2
-dppf)] [Pt–S–C 107.8(2)° and 109.7(2)°] and [Pt(SPr)2
(j2
-dppf)] [Pt–S–C 105.2(4)° and 107.4(3)°] [21].
Fe
P
P
M
Cl
Cl
Ph2
Ph2
Fe
P
P
M
Ph2
Ph2
NN
E
KS Ph
N
N
E
S
Ph
N
N
E
S
Ph
2
EtOH/CHCl3
1 M = Pd, E = O
2 M = Pt, E = O
3 M = Pd, E = NPh
E = O, Phozt
E = NPh, Ph2tzt
Scheme 1.
Fig. 1. Molecular structure of [Pt(Phozt)2(j2
-dppf)] (2): hydrogen atoms are
omitted and only the labels of the ipso C atoms of the phenyl and cyclopentadienyl
rings are represented for clarity, selected bond lengths (Å) and angles (°); Pt–P(1)
2.305(1), Pt–P(2) 2.317(1), Pt–S(1) 2.406(1), Pt–S(2) 2.370(1), C(2)–N(2) 1.308(7),
C(10)–N(4) 1.335(7), N(1)–N(2) 1.420(6), N(3)–N(4) 1.396(7), S(1)–Pt–S(2)
85.25(4), P(1)–Pt–P(2) 98.08(5), Pt–S(1)–C(2) 99.8(2), Pt–S(2)–C(10) 99.9(2).
22 S.A. Al-Jibori et al. / Polyhedron 41 (2012) 20–24
4. As detailed in Section 1, we have previously found that com-
plexes [ML2{j2
-Ph2P(CH2)nPPh2}] (L = bztzt and bzoxt) exist as a
mixture S- and N-bound isomers [13]. We have now prepared the
related dppf complexes [M(bztzt)2(j2
-dppf)] (4–5) and [Pd(bzoxt)2
(j2
-dppf)] (6) as red-brown (M = Pd) or yellow (M = Pt) solids in
73–91% yields upon simple addition of Kbztzt [34] or Kbzoxt [35]
to [MCl2(j2
-dppf)] (Scheme 2). Again all showed a single resonance
in the 31
P{1
H} NMR spectrum and for [Pt(bztzt)2(j2
-dppf)] (5) the
JPt–P coupling constant of 3264 Hz was strongly indicative of the
sulfur-bound coordination of the new ligands [36]. An X-ray crystal
structure of 6 confirmed this, the results of which are summarized
in Fig. 2. The overall geometry is very similar to that found in 2. Pal-
ladium–sulfur distances are within the expected ranges and the
dppf ligand subtends a bite-angle of 96.45(3)°. The two thionate li-
gands are now slightly further apart, the S(1)–Pd–S(2) angle being
89.64(3)°, and again the substituents lie on opposite sides of the
PdS2P2 plane (anti-conformation). Unlike in 2 and related platinum
bis(thiolate) complexes, the angles at sulfur now vary significantly
at 96.15(12)° and 107.21(12)°. The reasons for this are not immedi-
ately clear.
4. Conclusions
We have shown in this work that palladium and platinum dppf
complexes with heterocyclic thionates are easily prepared and
purified with all existing in the sulfur-bound thiolate form (Chart
1). This is in contrast to related complexes with diphosphines with
methylene backbones for which mixtures of sulfur- and nitrogen-
bound linkage isomers are observed. The reasons for this difference
are not immediately obvious but possibly relate to the more flexi-
ble nature of the dppf ligand and its greater steric demands.
Appendix A. Supplementary material
CCDC 767746 and 767747 contain the supplementary crystallo-
graphic data for 2 and 6, respectively. These data can be obtained
free of charge via http://www.ccdc.cam.ac.uk/conts/retriev-
ing.html, or from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336 033; or
e-mail: deposit@ccdc.cam.ac.uk.
References
[1] E.S. Raper, Coord. Chem. Rev. 161 (1985) 115.
[2] E.S. Raper, Coord. Chem. Rev. 129 (1994) 91.
[3] P.D. Akrivos, Coord. Chem. Rev. 213 (2001) 181.
[4] T.S. Lobana, Proc. Indian Acad. Sci. (Chem. Sci.) 112 (2000) 23.
[5] N.A. Bell, S.J. Coles, C.P. Constable, D.E. Hibbs, M.B. Hursthouse, R. Mansor, E.S.
Raper, C. Sammon, Inorg. Chim. Acta 323 (2001) 69.
[6] P. Aslanidis, P.J. Cox, S. Divanidis, P. Karagiannidis, Inorg. Chim. Acta 357 (2004)
4231.
[7] E. Marchesi, A. Marchi, L. Marvelli, M. Peruzzini, M. Bruganti, V. Bertolasi, Inorg.
Chim. Acta 358 (2005) 352.
[8] S.A. Al-Jibori, I.N. Al-Nassiri, L.J. Al-Hayaly, Transition Met. Chem. 27 (2002)
191.
[9] A.M. Qadir, A.I. Abdullah, S.A. Al-Jibori, T.A.K. Al-Allaf, Asian J. Chem. 16 (2004)
1180.
[10] O.H. Amin, L.J. Al-Hayaly, S.A. Al-Jibori, T.A.K. Al-Allaf, Polyhedron 23 (2004)
2013.
[11] B.H. Abdullah, M.A. Abdullah, S.A. Al-Jibori, T.A.K. Al-Allaf, Asian J. Chem. 19
(2007) 1334.
[12] B.H. Abdullah, S.A. Al-Jibori, M.A. Abdullah, T.A.K. Al-Allaf, Asian J. Chem. 19
(2007) 2307.
[13] S.A. Al-Jibori, A.S.S. Al-Zaubai, M.Y. Mohammed, T.A.K. Al-Allaf, Transition Met.
Chem. 32 (2007) 281.
[14] D.A. Clemente, G. Pilloni, B. Corain, B. Longato, M. Tiripicchino-Camellini,
Inorg. Chim. Acta 115 (1986) L9.
[15] B. Corain, B. Longato, G. Favero, D. Ajo, G. Pilloni, U. Russo, F.R. Kreissl, Inorg.
Chim. Acta 157 (1989) 259.
[16] L.T. Phang, S.C.F. Au-Yeyng, T.S.A. Hor, S.B. Khoo, Z.Y. Zhou, T.C.W. Mak, J.
Chem. Soc., Dalton Trans. (1993) 165.
[17] G.M. Delima, C.A.L. Filgueiras, M.S. Gitto, Y. Mascarenhas, Transition Met.
Chem. 20 (1995) 380.
[18] S. Otto, A. Roodt, Acta Crystallogr., Sect. C 35 (1997) 1414.
[19] G. Bandoli, A. Dolmella, Coord. Chem. Rev. 209 (2000) 161.
[20] T.A.K. Al-Allaf, H. Schmidt, K. Merzweiler, C. Wagner, D. Steinborn, J.
Organomet. Chem. 678 (2003) 48.
Fe
P
P
M
Cl
Cl
Ph2
Ph2
N
X
KS2
EtOH/CHCl3
Fe
P
P
M
Ph2
Ph2
NX
S
N
X
S
4 M = Pd, X = S
5 M = Pt, X = S
6 M = Pd, X = O
X = S, bztzt
X = O, bzoxt
Scheme 2.
Fig. 2. Molecular structure of [Pd(bzoxt)2(j2
-dppf)] (6): hydrogen atoms are
omitted and only the labels of the ipso C atoms of the phenyl and cyclopentadienyl
rings are represented for clarity, selected bond lengths (Å) and angles (°); Pd–P(1)
2.324(8), Pd–P(2) 2.3213(8), Pd–S(1) 2.3769(8), Pd–S(2) 2.3644(8), C(1)–N(1)
1.305(5), C(8)–N(2) 1.297(4), S(1)–Pd–S(2) 89.64(3), P(1)–Pd–P(2) 96.45(3), Pd–
S(1)–C(1) 107.21(12), Pd–S(2)–C(8) 96.15(12).
S.A. Al-Jibori et al. / Polyhedron 41 (2012) 20–24 23
5. [21] W.S. Han, Y.-J. Kim, S.W. Lee, Bull. Kor. Chem. Soc. 24 (2003) 60.
[22] V.D. De Castro, G.M. De Lima, A.O. Porto, H.G.L. Helmuth, J.D. De Souza Filno,
J.D. Ayala, G. Bombieri, Polyhedron 23 (2004) 63.
[23] K.H. Al-Obaidi, A.H. Jassim, N. Raasoul, Z.A. Muhi-Elden, Iraqi J. Sci. 31 (1990)
128.
[24] R.W. Young, K.H. Wood, J. Am. Chem. Soc. 77 (1955) 400.
[25] J.H. Price, A.N. Williamson, R.F. Schramm, B.B. Wagland, Inorg. Chem. 11
(1972) 1280.
[26] IPDS – Software Package, Stoe Cie, 1999.
[27] G.M. Sheldrick, SHELXS-97, Program for Crystal Structure Solution, Göttingen,
1997.
[28] G.M. Sheldrick, SHELXL-97, Program for the Refinement of Crystal Structures,
Göttingen, 1997.
[29] K. Branderburg, Diamond, Release 2, Crystal Impact, GbR, Bonn, 1997.
[30] M.Y. Mhasalkar, M.H. Shah, S.T. Nikam, K.G. Anantanarayanan, C.V. Deliwala, J.
Med. Chem. 13 (1970) 672.
[31] N. Begum, U.K. Das, M. Hassan, G. Hogarth, S.E. Kabir, E. Nordlander, M.A.
Rahman, D.A. Tocher, Organometallics 26 (2007) 6462.
[32] S.-K. Lee, D.-Y. Noh, Inorg. Chem. Commun. 13 (2010) 183.
[33] D.-Y. Noh, E.-M. Seo, H.-J. Lee, H.-Y. Jang, M.-G. Choi, Y.H. Kim, J. Hong,
Polyhedron 20 (2001) 1939.
[34] N. Singh, A. Prasad, R.K. Sinha, Bull. Chem. Soc. Jpn. 82 (2009) 81.
[35] T. Yoshida, Bull. Chem. Soc. Jpn. 53 (1980) 1449.
[36] E. Colocio, R. Cuesta, M. Ghazi, M.A. Huertas, J.M. Moreno, A. Navarrete, Inorg.
Chem. 36 (1997) 1652.
24 S.A. Al-Jibori et al. / Polyhedron 41 (2012) 20–24