|
| ||
|
|
||
Bulky Substituents (bulky + substituent)
Selected AbstractsPyrazolate-Based Dinucleating Ligands in L2M2 Scaffolds: Effects of Bulky Substituents and Coligands on Structures and M···H,C InteractionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2004Jens C. Röder Abstract A series of nickel(II) and palladium(II) complexes [L2M2]2+ have been prepared and structurally characterized, where L is a pyrazolate ligand with bulky 2,6-dimethyl- or 2,6-di(isopropyl)anilinomethyl side arms. Coordinating counter anions such as chloride can bind to axial sites of the dinickel species in a solvent-dependent process, giving rise to five-coordinate high-spin metal ions. In the case of weakly coordinating anions, the metal ions are found in roughly square-planar environments, and the structures are governed by the tendency of the bulky aryl groups to avoid each other, which forces the methyl or isopropyl substituents in the aryl 2- and 6-positions to approach the metal ions from the axial directions. This leads to drastic low-field shifts of the respective 1H NMR signals, e.g. , = 7.86 ppm for the isopropyl ,CH which comes in close proximity to the low-spin nickel(II) center. The relevance of such low-field NMR resonances of protons close to the axial sites of d8 metal ions for possible three-center four-electron M···H,C hydrogen bonds involving the filled d orbital of the metal ion is discussed. In the present case, attractive M···H interactions are assumed to be of no major significance. This was corroborated by the structure of a further [L2Ni2]2+ type complex where the anilinomethyl side arms bear only a single 2-isopropyl group, which was found rotated away from the metal. Additional spectroscopic and electrochemical properties of the various complexes are reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Synthesis and Reactivity of 23 - tert -Butyl- and 23 -Phenyltetraarylazuliporphyrins: an Analysis of the Effect of Bulky Substituents on Oxidative Ring Contractions to Benzocarbaporphyrins,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 24 2007Jessica A. El-Beck Abstract 6- tert -Butyl- and 6-phenylazulene reacted with pyrrole and benzaldehyde in a molar ratio of 1:3:4 in the presence of BF3·Et2O in chloroform, followed by oxidation with DDQ, to give 23 -substituted tetraphenylazuliporphyrins in 15,20,% yield. Slightly higher yields of the related meso -tetrakis(4-chlorophenyl)azuliporphyrins were obtained using 4-chlorobenzaldehyde. The presence of an electron-donating tert -butyl substituent increased the diatropic character of the azuliporphyrin system as determined by the proton NMR chemical shifts for the internal CH resonance, while intermediary results were noted for 23 -phenylazuliporphyrins. Addition of TFA afforded dications with increased aromatic ring currents, but electron-donating substituents (tBu,>,Ph) again produced a larger upfield shift for the internal CH signal due to stabilization of the tropylium character that is required so that the system can attain carbaporphyrin-type aromaticity. The substituted azuliporphyrins reacted with nickel(II) acetate or palladium(II) acetate to give the corresponding organometallic derivatives. In addition, oxidations with tBuOOH and KOH afforded benzocarbaporphyrin products in approximately 50,% yield. The presence of tert -butyl or phenyl substituents did not block these oxidative ring contraction processes, and the rate of reaction was slightly increased compared to 23 -unsubstituted azuliporphyrins. The major products were 22 - tert -butyl or phenyl-substituted benzocarbaporphyrins and minor products with an additional formyl substituent were also isolated. These products are consistent with an initial nucleophilic addition occurring at the position adjacent to the R group on the azulene ring. Detailed mechanisms are proposed to explain these observations. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] ChemInform Abstract: Synthesis of Salicylaldehydes Bearing Bulky Substituents in the Position 3 and 5CHEMINFORM, Issue 19 2008A. I. Kochnev Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Silylation of Silyl- and Germylketenes Containing Bulky Substituents at the Silicon or Germanium Atom.CHEMINFORM, Issue 7 2002S. V. Ponomarev Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Efficient and Long-Living Light-Emitting Electrochemical CellsADVANCED FUNCTIONAL MATERIALS, Issue 9 2010Rubén D. Costa Abstract Three new heteroleptic iridium complexes that combine two approaches, one leading to a high stability and the other yielding a high luminescence efficiency, are presented. All complexes contain a phenyl group at the 6-position of the neutral bpy ligand, which holds an additional, increasingly bulky substituent on the 4-position. The phenyl group allows for intramolecular ,,, stacking, which renders the complex more stable and yields long-living light-emitting electrochemical cells (LECs). The additional substituent increases the intersite distance between the cations in the film, reducing the quenching of the excitons, and should improve the efficiency of the LECs. Density functional theory calculations indicate that the three complexes have the desired ,,, intramolecular interactions between the pendant phenyl ring of the bpy ligand and the phenyl ring of one of the ppy ligands in the ground and the excited states. The photoluminescence quantum efficiency of concentrated films of the complexes improves with the increasing size of the bulky groups indicating that the adopted strategy for improving the efficiency is successful. Indeed, LEC devices employing these complexes as the primary active component show shorter turn-on times, higher efficiencies and luminances, and, surprisingly, also demonstrate longer device stabilities. [source] Versatile Self-Complexing Compounds Based on Covalently Linked Donor,Acceptor CyclophanesCHEMISTRY - A EUROPEAN JOURNAL, Issue 1 2005Yi Liu Dr. Abstract A range of covalently linked donor,acceptor compounds which contain 1) a hydroquinone (HQ) unit, 2) a 1,5-dioxynaphthalene (DNP) ring system, or 3) a tetrathiafulvalene (TTF) unit as the ,-donor, and 4) cyclobis(paraquat- p -phenylene) (CBPQT4+) as the ,-accepting tetracationic cyclophane were prepared and shown to operate as simple molecular machines. The ,-donating arms can be included inside the cyclophane in an intramolecular fashion by virtue of stabilizing noncovalent bonding interactions. What amounts to self-complexing/decomplexing equilibria were shown to be highly temperature dependent when the ,-donating arm contains either an HQ or DNP moiety. The thermodynamic parameters associated with the equilibria have been unraveled by using variable-temperature 1H NMR spectroscopy. The negative ,H° and ,S° values account for the fact that the "uncomplexed" conformation becomes the dominant species, since the entropy gain associated with the decomplexation process overcomes the enthalpy loss resulting from the breaking of the donor,acceptor interactions. The arm's in-and-out movements with respect to the linked cyclophanes can be arrested by installing a bulky substituent at the end of the arm. In the case of compounds carrying a DNP ring system in their side arm, two diastereoisomeric, self-complexing conformations are observed below 272 K in hexadeuterioacetone. By contrast, control over the TTF-containing arm's movement is more or less ineffective through the thermally sensitive equilibrium although it can be realized by chemical and electrochemical ways as a result of TTF's excellent redox properties. Such self-complexing compounds could find applications as thermo- and electroswitches. In addition, the thermochromism associated with the arm's movement could lead to some of the compounds finding uses as imaging and sensing materials. [source] Catalytic Trimerization of Ethylene with Highly Active Half-sandwich Titanium Complexes Bearing Pendant p -Fluorophenyl GroupsCHINESE JOURNAL OF CHEMISTRY, Issue 10 2006Chen Wang Abstract Two new complexes [,5 -C5H4CMe2 -(p -fluorophenyl)]TiCl3 (1) and [,5 -C5H4C(cyclo-C5H10)-(p -fluoro-phenyl)]TiCl3 (2) were synthesized and characterized. Their activities and selectivities for trimerization of ethylene were investigated. The introduction of fluorine atom greatly weakened the arene coordination, but this disadvantageous factor can be eliminated by introduction of a bulky substituent, such as cyclo-C5H10, to the bridging carbon linked to the Cp ring. The combinative effect of the fluorine substitute and the bridging unit can make complex 2 as a highly active and selective catalyst for ethylene trimerization. Its productivity and selectivity for 1-hexene can reach 1024.0 kg·mol,1·h,1 and 99.3% respectively. [source] Improved synthesis of DOTA tetraamide ligands for lanthanide(III) ions: A tool for increasing the repertoire of potential PARACEST contrast agents for MRI and/or fluorescent sensorsCONTRAST MEDIA & MOLECULAR IMAGING, Issue 3 2010Luis M. De León-Rodríguez Abstract The synthesis of new DOTA tetraamide (DOTAMR4) compounds is of great interest given their application in the formation of Ln(III) complexes as potential PARACEST contrast agents in MRI or fluorescent molecular probes. In this context amino acid and peptide DOTAMR4 derivatives are particularly attractive since the amino-acid and/or peptide moiety can show responsive properties dependent on a given stimuli which might translate to changes in water exchange rates of the corresponding Ln(III) complex. Current synthesis of DOTAMR4 derivatives is typically carried out by reacting haloacetamide intermediates with cyclen. However, this method fails to generate the tetra-substituted products when bulky substituents are present in the haloacetamide and in some cases this intermediate cannot be prepared by conventional acylation procedures limiting the number of DOTAMR4 compounds available for study. As a solution to these limitations, an improved methodology for the synthesis of DOTAMR4 by coupling DOTA to an appropriate amine containing reagent (i.e. protected amino-acids with the , -amino group free) is presented in this work. Several DOTAMR4 derivatives which are difficult or impossible to prepare with the traditional methodologies were easily obtained starting with DOTA. A new protocol was derived using this methodology for the solution-phase synthesis of DOTA peptide derivatives. With this methodology, many other DOTAMR4 peptide and non-peptide derivatives have been prepared in our laboratories with several of these new compounds showing interesting properties for molecular imaging. Copyright © 2010 John Wiley & Sons, Ltd. [source] Bulky Pyrazolate-Based Compartmental Ligand Scaffolds: Encapsulation of an Edge-Sharing Cu6O2 Bitetrahedral Core,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 34 2008Anna Sachse Abstract Upon reaction with Cu(OAc)2·H2O, pyrazole-based ligands with two appended imine chelate arms in the 3- and 5-positions of the pyrazole and bulky substituents at the imine-N yield Cu6 complexes [L2Cu6(,-OAc)6(,4 -O)2] (1a,b). They feature an unusual {Cu6(,4 -O)2}-bitetrahedral core, only the second example of this structural motif. ESI mass spectrometric and UV/Vis data confirm that the Cu6 complexes stay intact in solution, and magnetic and high-field EPR measurements reveal an S = 0 ground state with the first excited triplet at ,E , 95 cm,1. Although the new hexanuclear systems are too complex for deriving all individual exchange constants from powder susceptibility data, a rough idea of the complete energy level spectrum could be obtained.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Aiding Factors in the Formation of Azaplatinacyclobutane Rings , X-ray and Crystal Structure of [Pt{CH(Ph)CH2NEt2 -,C,,N}(N,N,N,,N, -tetramethylethylenediamine)]+ and of Its Open-Chain PrecursorEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2007Giuseppe Lorusso Abstract The addition products 2 of a secondary amine to a coordinated olefin, in the cationic complexes [PtCl(,2 -CH2=CHR)(tmeda)]+ (tmeda = N,N,N,,N, -tetramethylethylenediamine; R = Me, 1a; Ph, 1b, H, 1c), undergo in basic medium an intramolecular nucleophilic substitution with elimination of the chlorido ligand and formation of an azaplatinacyclobutane ring 3. The ring-closing process occurs notwithstanding the absence of a labilizing ligand trans to the leaving chlorido ligand and of bulky substituents on the amino,ethanide chain. If the addition product 2 is a mixture of Markovnikov and anti-Markovnikov isomers, the ring-closing reaction is faster for the anti-Markovnikov form, and this leads to an increase of the relative amount of the anti-Markovnikov isomer in the cyclized species 3. The difference in the rate of formation of the azaplatinacyclobutane ring between the two isomers has been interpreted on the basis of a more favorable stereochemistry in the case of the anti-Markovnikov form. The X-ray crystal structures of [Pt{CH(Ph)CH2NEt2 -,C,,N}(tmeda)]+ (3bn) and of its open-chain precursor, [PtCl{CH(Ph)CH2NHEt2}(tmeda)]+ (2bn) fully support this hypothesis.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Facile Construction of Spirocyclopropanated Bi-, Tri- and Tetracyclic Skeletons by Novel Cascades Involving Intra- and Intermolecular Heck Reactions of 2-Bromo-1,6-enynes and BicyclopropylideneEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 3 2005Michael Schelper Abstract Acyclic 2-bromo-1,6-enynes 5 -R, 9 -R and 11 -R with bulky substituents at the acetylenic terminus were co-cyclized with the highly strained bicyclopropylidene (12) under palladium catalysis at 80 °C to give the cross-conjugated tetraenes 13 -R, 18 -R and 19 -R in moderate-to-good yields (34,71%). Only the co-cyclization of 5 -Ph gave rise to an additional product, which was identified as the 11-membered ring 20. At elevated temperatures (120,140 °C) the initially formed tetraenes underwent 6,-electrocyclization to give spiro[cyclopropane-1,4,-bicylo[4.3.0]-1(6),2-dienes] 21 -R, 22 -R and 23 -R. This novel class of spirocyclopropanated oligocycles is also accessible by a one-pot protocol. The highest yields for both the tetraenes and bicyclo[4.3.0]nonadiene and its heteroanalogues were obtained with bulky substituents at the alkyne terminus of the precursors. Heteroatom-containing precursors 9 -R and 11 -R gave lower yields than their all-carbon analogues 5 -R. The acyclic 2-bromo-1,8-dien-6-ynes 28a,b,c upon palladium-catalyzed co-cyclization with bicyclopropylidene (12) at 110 °C gave spirocyclopropanated tricycles 31a,b and 32, respectively, in moderate yields (14, 31 and 32%). These products were formed by two consecutive 6,-electrocyclizations. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Ionic Iridium(III) Complexes with Bulky Side Groups for Use in Light Emitting Cells: Reduction of Concentration QuenchingADVANCED FUNCTIONAL MATERIALS, Issue 13 2009Carsten Rothe Abstract Here, the photophysics and performance of single-layer light emitting cells (LECs) based on a series of ionic cyclometalated Ir(III) complexes of formulae and where ppy, bpy, and phen are 2-phenylpyridine, substituted bipyridine and substituted phenanthroline ligands, respectively, are reported. Substitution at the N,N ligand has little effect on the emitting metal-ligand to ligand charge-transfer (MLLCT) states and functionalization at this site of the complex leads to only modest changes in emission color. For the more bulky complexes the increase in intermolecular separation leads to reduced exciton migration, which in turn, by suppressing concentration quenching, significantly increases the lifetime of the excited state. On the other hand, the larger intermolecular separation induced by bulky ligands reduces the charge carrier mobility of the materials, which means that higher bias fields are needed to drive the diodes. A brightness of ca. 1000,cd,m,2 at 3,V is obtained for complex 5, which demonstrates a beneficial effect of bulky substituents. [source] Spontaneous Formation of Complex Periodic Superstructures under High Interferential Illumination of Small-Molecule-Based Photochromic MaterialsADVANCED FUNCTIONAL MATERIALS, Issue 5 2009Eléna Ishow Abstract A series of push-pull azo compounds containing bulky substituents are synthesized, yielding fully amorphous materials with glass-transition temperatures above 200,°C. Thin films are subjected to holographic illumination and show superior bulk photomigration in terms of speed and efficiency compared to materials exhibiting similar electronic and photochromic properties in the solid state. The reported results give evidence that a microscopic consideration of the free volume rather than macroscopic parameters like the glass-transition temperature should to be adopted to interpret the matrix stiffness and its deformation ability. Irradiation performed at higher laser intensity produces periodic superstructures whose height is five to six times as high as the initial film thickness. The surface tension and instability effects are put forward to interpret the growth of such superstructures. [source] Catalytic 1,2-Dicyanation of Alkynes by Palladium(II) under Aerobic ConditionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2009Shigeru Arai Abstract A stereoselective 1,2-dicyanation of various alkynes in the presence of trimethylsilyl cyanide (TMSCN) by palladium(II) catalysis under aerobic conditions is investigated. This reaction includes two cyanation pathways, syn - and anti -cyanopalladation to alkynes that are activated by Pd(II). High syn -selectivity was observed in the reaction using terminal alkynes that have bulky substituents at a propargyl position and aliphatic internal alkynes. Furthermore, a dramatic acceleration was observed with substrates having an N -arenesulfonyl functionality at a propargyl position, this indicates that both sulfoxide and carbon-carbon triple bond act as Lewis bases to Pd(II). [source] Reaction of Bis(alkynyl)silanes with Tris(pentafluorophenyl)borane: Synthesis of Bulky Silole Derivatives by Means of 1,1-Carboboration under Mild Reaction ConditionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 7-8 2009Gereon Dierker Abstract The strong Lewis acid tris(pentafluorophenyl)borane [B(C6F5)3] reacts rapidly with dimethylbis(phenylethynyl)silane (1c) at room temperature in toluene by shift of a pentafluorophenyl (C6F5) group and formation of a new carbon-bis(pentafluorophenyl)boron linkage [CB(C6F5)2] in a sequence of 1,1-carboboration reactions to yield the 4-bis(pentafluorophenyl)boryl/3-pentafluorophenyl-substituted 1,1-dimethyl-2,5-diphenylsilole derivative 7c. The analogous reaction of bis(trimethylsilylethynyl)diphenylsilane (1d) with tris(pentafluorophenyl)borane gave the corresponding boryl-substituted silole derivative (7d) featuring six bulky substituents attached at the central heterocyclic framework. Both the starting materials (1c, 1d) and the products (7c, 7d) were characterized by X-ray crystal structure analyses. [source] Ring transformations of heterocyclic compounds.JOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 2 20022,4,6-Triarylpyrylium perchlorates 1 react with methyleneindolines 3in situ generated from the corresponding methylindolium salts 2, which are spiro-fused with a cycloalkane, benzanellated cycloalkene or a heterocyclic system. These diastereoselective 2,5-[C4+C2] pyrylium ring transformations are carried out in the presence of triethylamine/acetic acid in boiling ethanol to give the dispiroindolines 4 with a trans configuration of the more bulky substituents at the cyclohexadiene ring. By the same type of transformation the dispiro compounds 7/10 with an additional fused benzene ring are obtained from the pyrylium salt 1a and 6/9, the benzo-fused analogues of 3. Spectroscopic data of the transformation products as well as their mode of formation are discussed. [source] Structure correlation study of four-coordinate copper(I) and (II) complexesACTA CRYSTALLOGRAPHICA SECTION B, Issue 3 2000Paul R. Raithby The geometries of four-coordinate CuI and CuII complexes in the Cambridge Structural Database (CSD) have been analysed systematically and compared using symmetry-deformation coordinates and principal component analysis. The observed stereochemistries have been rationalized in terms of the d -electron configurations, interligand repulsion and ,-bonding effects. The results confirm that the majority of four-coordinate copper(I) complexes in the CSD adopt tetrahedral geometries and deviations from tetrahedral symmetry are caused by the presence of chelating ligands or by the incorporation of copper centres into dimeric or polymeric structures. Four-coordinate copper(II) complexes generally adopt geometries close to square planar; this is particularly evident for bis(chelate) complexes where ,-bonding is important. Distortions towards tetrahedral geometries are attributable to steric interactions of bulky substituents in the bidentate ligands. [source] Titanium complexes with sulfur-linked bis(phenolate) ligandsACTA CRYSTALLOGRAPHICA SECTION C, Issue 11 2009Thomas S. Dols High-quality crystals of two bis(phenolate)titanium complexes, namely dichlorido{4,4,-dimethyl-2,2,-[cyclohexane-1,2-diylbis(sulfanediyl)]diphenolato}titanium(IV), [Ti(C20H22O2S2)Cl2], (I), and dichlorido{2,2,-[cyclohexane-1,2-diylbis(sulfanediyl)]diphenolato}titanium(IV), [Ti(C18H18O2S2)Cl2], (II), were obtained by reactive crystallization. Depending on the solvent, compound (II) was obtained as unsolvated (IIa) or as the toluene hemisolvate, [Ti(C18H18O2S2)Cl2]·0.5C7H8, (IIb). These systems without bulky substituents on the aromatic phenolate rings serve as ideal model compounds for precatalysts. The excellent X-ray diffraction data will help clarify the nature of the mismatched interactions between the soft S atoms within the ligand and the hard titanium center. Molecule (I) has crystallographic C2 symmetry. [source] Fine-Tuning the Dimerization of Tetraureacalix[4]arenesCHEMISTRY - A EUROPEAN JOURNAL, Issue 15 2010Yuliya Rudzevich Dr. Abstract Calix[4]arenes substituted by four urea residues at their wide rim form hydrogen-bonded homo- and heterodimeric capsules in apolar solvents. If urea groups are covalently connected to loops or substituted by bulky residues, the dimerization may be restricted to those pairs in which the loops do not overlap and for which the residues are small enough to pass the loops. In the present study, we describe the dimerization properties of tetraureas with one, two (adjacent or opposite), three, or four loops and those bearing (additionally) up to four residues of different size: a=tolyl, b=3,5-di- tert -butylphenyl, c=4-propyloxy-3,5-di-(tert -butylphenyl)phenyl, and d=4-[tris-(4- tert -butylphenyl)methyl]phenyl. For compounds with four loops of different size (O(CH2)nO-chains with n=10, 14, and 20 connecting the m -positions of the urea phenyl residues) a clear "stepwise" sorting scheme could be established, in which the bulkiest residue d is excluded by all tetraloop compounds and the smallest residue a can pass only the smallest loops (n=10). The medium-sized residues b or c are tolerated by n=14 and 20 or only by n=20. Selectivities can be built up also on geometrical factors. A trisloop compound, for instance, combines only with a tetraurea bearing a single bulky residue and tetraureas with two bulky substituents in adjacent or opposite position are distinguished by the bisloop derivatives with adjacent or opposite loops. The impossibility to form a homodimer of a monoloop compound containing two bulky residues leads to its selective heterodimerization with a derivative bearing three bulky groups. Subtle effects for "borderline" cases, in which the dimerization or reorganization takes a longer time, are also discussed. [source] Gold(I)-Catalyzed Intermolecular Hydroarylation of Alkenes with Indoles under Thermal and Microwave-Assisted ConditionsCHEMISTRY - A EUROPEAN JOURNAL, Issue 27 2008Ming-Zhong Wang Abstract An efficient method for intermolecular hydroarylation of aryl and aliphatic alkenes with indoles using a combination of [(PR3)AuCl]/AgOTf as catalyst under thermal and microwave-assisted conditions has been developed. The gold(I)-catalyzed reactions of indoles with aryl alkenes were achieved in toluene at 85,°C over a reaction time of 1,3,h with 2,mol,% of [(PR3)AuCl]/AgOTf as catalyst. This method works for a variety of styrenes bearing electron-deficient, electron-rich, and sterically bulky substituents to give the corresponding products in good to high yields (60,95,%). Under microwave irradiation, coupling of unactivated aliphatic alkenes with indoles gave the corresponding adducts in up to 90,% yield. Selective hydroarylation of terminal CC bond of conjugated dienes with indoles gave good product yields (62,81,%). On the basis of deuterium-labeling experiments, a reaction mechanism involving nucleophilic attack of Au(I)-coordinated alkenes by indoles is proposed. [source] | |||||||||||||||||||||||||