Sulfur Donor Ligands Research Articles

Complexes of nickel(II) and palladium(II) with thiobenzamide

The electronic and vibrational spectra of NiII and PdII complexes with thiobenzamide, L, are discussed. L acts as a sulphur donor ligand. The PdII compounds and (NiL4)(ClO4)2 are square planar. PdL2Cl2 has acis-structure, while PdL2X2 (X=Br or I) istrans; NiL4Cl2 istrans-octahedral. The i.r. bands due toν(M.S) andν(MX) have been assigned. The influence of the anions on the properties of the complexes, both in solution and in the solid state, is discussed.

Spectroscopic and redox studies of some copper(II) complexes with biomimetic donor atoms: implications for protein copper centres

The redox chemistry and e.s.r. spectra of a number of copper(II) complexes with nitrogen- and sulphur-donor ligands have been examined, including complexes with 2,2′-bi-imidazole, histamine, and cyclic and acyclic saturated amine and thioether ligands. The tetrahedral CuIIS4 centre generated by γ-irradiation of single crystals of a thioacetamide complex of CuI has a low value of |A∥|. Tetrahedral distortion of otherwise tetragonal copper(II) centres increases g∥ and decreases |A∥| for N-, S-, and O-donor ligands, and is a more effective source of reduction of |A∥| than charge effects. The quotient g∥/|A∥| appears to be a convenient empirical index of distortion of the donor set from planar toward tetrahedral, indicating that most type I copper in proteins is tetrahedrally, rather than tetragonally, co-ordinated.

ChemInform Abstract: COMPLEXES WITH SULFUR AND SELENIUM DONOR LIGANDS. PART 7. THE CRYSTAL AND MOLECULAR STRUCTURE OF BIS(DIPHENYLPHOSPHINODITHIOATO)‐COBALT(II)‐QUINOLINE(1 1)

Chemischer InformationsdienstVolume 9, Issue 50 Physical Organic Chemistry ChemInform Abstract: COMPLEXES WITH SULFUR AND SELENIUM DONOR LIGANDS. PART 7. THE CRYSTAL AND MOLECULAR STRUCTURE OF BIS(DIPHENYLPHOSPHINODITHIOATO)-COBALT(II)-QUINOLINE(1 1) A. CHIESI VILLA, A. CHIESI VILLASearch for more papers by this authorC. GUASTINI, C. GUASTINISearch for more papers by this authorP. PORTA, P. PORTASearch for more papers by this authorA. A. G. TOMLINSON, A. A. G. TOMLINSONSearch for more papers by this author A. CHIESI VILLA, A. CHIESI VILLASearch for more papers by this authorC. GUASTINI, C. GUASTINISearch for more papers by this authorP. PORTA, P. PORTASearch for more papers by this authorA. A. G. TOMLINSON, A. A. G. TOMLINSONSearch for more papers by this author First published: December 12, 1978 https://doi.org/10.1002/chin.197850082Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume9, Issue50December 12, 1978 RelatedInformation

ChemInform Abstract: COMPLEXES WITH SULFUR AND SELENIUM DONOR LIGANDS. PART 6. KINETICS AND MECHANISM OF THE REACTION BETWEEN 1,2‐BIS(DIPHENYLPHOSPHINO)‐ETHANE AND TRIS(OO′‐DIMETHYL PHOSPHORODITHIOATO)COBALT(III)

Chemischer InformationsdienstVolume 9, Issue 50 Organoelement Compounds ChemInform Abstract: COMPLEXES WITH SULFUR AND SELENIUM DONOR LIGANDS. PART 6. KINETICS AND MECHANISM OF THE REACTION BETWEEN 1,2-BIS(DIPHENYLPHOSPHINO)-ETHANE AND TRIS(OO′-DIMETHYL PHOSPHORODITHIOATO)COBALT(III) E. BORGHI, E. BORGHISearch for more papers by this authorV. DI CASTRO, V. DI CASTROSearch for more papers by this authorF. MONACELLI, F. MONACELLISearch for more papers by this authorA. A. G. TOMLINSON, A. A. G. TOMLINSONSearch for more papers by this author E. BORGHI, E. BORGHISearch for more papers by this authorV. DI CASTRO, V. DI CASTROSearch for more papers by this authorF. MONACELLI, F. MONACELLISearch for more papers by this authorA. A. G. TOMLINSON, A. A. G. TOMLINSONSearch for more papers by this author First published: December 12, 1978 https://doi.org/10.1002/chin.197850302Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume9, Issue50December 12, 1978 RelatedInformation

Complexes with sulphur and selenium donor ligands. Part 6. Kinetics and mechanism of the reaction between 1,2-bis(diphenylphosphino)-ethane and tris(OO′-dimethyl phosphorodithioato)cobalt(III)

The kinetics and mechanism of the reaction between [Co{S2P(OMe)2)3] and Ph2P[CH2]2PPh2(dppe) in CH2CI2have been investigated by spectrophotometric and conductance methods. The reaction proceeds in two steps. The first step is (i), deduced from the formation of ions during the reaction and on spectroscopic grounds. The [Co{S2P(OMe)2}3]+ dppe →[Co{S2P(OMe)2}2(dppe)]++[S2P(OMe)2]–(i) activation parameters are ΔH‡= 14.3 ± 1.0 kcal mol–1 and ΔS+=–17 ± 3 cal K–1 mol–1. The low ΔS‡ value and linear dependence of the rate on dppe concentration suggests rate-determining nucleophilic participation of the incoming ligand. A one-ended reversible dissociation of the dithioate ligand with the dppe competing for the resulting five-co-ordinate intermediate or direct nucleophilic attack of the phosphine on [Co{S2P(OMe)2}3] or on the dithioate phosphorus are mechanisms consistent with the data. The second step of the reaction is (ii). [Co{S2P(oMe)2}2(dppe)]++[S2P(OMe)2]–→[Co{S2P(OMe)2}{S2PO(OMe)}(dppe)]+ P(OMe)2S(SMe)(ii) Although a reliable estimate of the rate constants could not be obtained because of ion-producing side reactions after ca. 90% completion of reaction, it is probable that this step occurs via nucleophilic attack on the P–O–C carbon atom of the co-ordinated [S2P(OMe)2]–.

Complexes with sulphur and selenium donor ligands. Part 7. The crystal and molecular structure of bis(diphenylphosphinodithioato)-cobalt(II)–quinoline (1/1)

The title complex has been characterised and its crystal and molecular structure solved by diffractometric methods. Turquoise crystals of formula [Co(S2PPh2)2]·C9H7N obtained from chloroform solution are orthorhombic, space group Fdd2, with unit-cell dimensions a= 23.528(2), b= 28.690(2), c= 9.571(1)A, and Z= 8. The structure has been refined by least-squares methods using 964 independent reflections, to a conventional R of 0.065. The structure is monomeric and the co-ordination about the cobalt is slightly distorted trigonal bipyramidal, the quinoline molecule lying in the equatorial plane. The axial and equatorial Co–S distances are very different, (Co–Sax)-(Co–Seq)= 0.30 A(3σ 0.018 A). This difference is reflected in the shorter P–Sax distance, which although just statistically significant (0.04 A shorter than P–Seq., 3σ 0.018 A). leads to an observable difference in the νasym(PS) band in the i.r. spectrum of the quinoline adduct and the parent [Co(S2PPh2)2]. The electronic spectra and magnetism of the complex are briefly discussed.

Complexes with sulphur and selenium donor ligands. Part 8. Some 4-phenylthiosemicarbazone complexes of cobalt(II) and the crystal structure of bis(acetone 4-phenylthiosemicarbazone)cobalt(II) bromide (green form)

Some thiosemicarbazone complexes of CoII of general formula CoL2X2 and Co(L – H)2(L = NHPh·CS·NH·N:CR1R2; X = Cl, Br, or I) have been prepared and characterised by spectroscopic methods in the solid state and in some non-aqueous solutions. When R1 and/or R2 is an aryl group the ligand is unidentate and tetrahedral complexes are obtained. When R1 and R2 are alkyl groups the ligand is bidentate and trigonal-bipyramidal complexes [CoL2X]X are obtained. Phenyl substitution at position 4 of the thiosemicarbazone thus seems to exert little effect on the stereochemistry adopted, and the complexes are similar to those of the unsubstituted ligand analogues. The crystal structure of the green form of [Co(NHPh·CS·NH·N:CMe2)Br]Br has been determined. Crystals are orthorhombic, space group Fddd, with unit-cell dimensions a= 17.039(3), b= 24.184(8), c= 24.852(7)A, and Z= 16. The structure has been solved by Patterson and Fourier methods from automatic diffractometer data and refined by least-squares techniques to R 0.077 from 612 independent non-zero reflections. The ligands are bidentate, the co-ordination about CoII being trigonal bipyramidal of chromophore [CoS2N2Br], with two sulphur atoms and the bromine atom lying in the trigonal plane. Possible structures for these complexes in solution and for some corresponding thiocyanates containing unsubstituted thiosemicarbazones are briefly discussed.

Complexes with sulphur and selenium donor ligands. Part V. Some Co(II) complexes with bidentate and monodentate unsubstituted thiosemicarbazones

Some thiosemicarbazone complexes of Co(II) halides, of general formula CoL 2X 2 (L = NH 2C(S)NHNCR 1R 2; R 1 = R 2 = Me; R 1 = Me, R 2 = Ph; R 1R 2 = cyclohexanone; R 1 = H, R 2 = Ph) have been prepared and characterised. From spectroscopic data it is concluded that when R 1 and/or R 2 is an aryl group, the structure in the solid state is tetrahedral of chromophore [CoS 2X 2] the ligands being monodentate. When R 1 = R 2 = Me or cyclohexanone, the solid state structure is trigonal bipyramidal. Independent crystal structure analyses for two examples, Co(NH 2C(S)NHNCMe 2) 2Cl 2·H 2O and Co(NH 2C(S)NHNCMePh) 2I 2 have confirmed these assignments. Possible structures present in solution are discussed.

Mercury (II) Thiosalicylic Acid (TSA) Complexes with Nitrogen and Sulfur Donor Ligands

Mercury (II) Thiosalicylic Acid (TSA) Complexes with Nitrogen and Sulfur Donor Ligands

Complexes of Tertiary Thioamides: Part III: Complexes of Dimethyl‐Thioacetamide with Co(II), Pd(II), Zn(II), Cd(II) and Hg(II)

AbstractComplexes of dimethyl‐thioacetamide (DMTA or L) with Co(II), Pd(II), Zn(II), Cd(II) and Hq(II) have been prepared and investigated by conductivity measurements, and by electronic, infrared and Raman spectroscopy. mL2Cl2 (M=Co, Zn, Hg), ML2I2 (M=Co, Zn, Cd, Hg) and [ML4] (ClO4)2 (M=Co, Zn, Cd) complexes are shown to be tetrahedral. CdLcl2 is polymeric, but a definite structure could not be assigned. Pd(II) forms planar cis‐PdL2Cl2, trans‐PdL2I2 and [PdL4] (ClO4)2. DMTA acts in all cases as a monodentate sulphur donor ligand.

Perfluoroalkyl derivatives of chromium and cobalt containing sulphur donor ligands

Perfluoroalkyl derivates of chromium (III) have been prepared containing dithiocarbamate ligands, e.g. R fCr(DTC) 2py. The complexes have a cis arrangement of pyridine and R f groups as determined by the X-ray crystal structure determination of C 3F 7Cr(Me 2NCS 2) 2py. An analogous cobalt(III) complex C 3F 7Co(Et 2NCS 2) 2py has also been prepared in small yield and 19F NMR measurements indicate a similar structure.

The reactions of dinitrogen complexes of molybdenum with thiols and sulphenyl halides

The dinitrogen complex trans-[Mo(N2)2dpe)2](dpe = Ph2PCH2CH2PPh2) reacts with thiols RSH (R = Et, Prn, Bun, or Ph) in tetrahydrofuran (thf) to give the diamagnetic complexes [Mo(SR)2(dpe)2], together with dihydrogen and two mole equivalents of dinitrogen. trans-[Mo(N2)2(depe)2](depe = Et2PCH2CH2PEt2) gives [Mo(SPh)2(depe)2] with thiophenol. With PhSCl, trans-[Mo(N2)2(dpe)2] gives [MoCl(SPh)(dpe)2] and 2N2, but with an excess of PhSBr, [MoBr2(dpe)2]Br3 results. The dithio-complexes act as bidentate sulphur-donor ligands and the paramagnetic thio-bridged binuclear complexes [(dpe)2Mo(SR)2MoCl4] and [(dpe)2Mo(SBun)2MoCl3(thf)]Cl (R = Ph, Et, Prn, and Bun) have been prepared, whose magnetic moments indicate bond formation between molybdenum atoms. The diamagnetic adduct [(dpe)2Mo(SBun)2Mo(CO)4] has also been obtained.

Chemistry of sulfur-donor ligand ortho-metalated iron carbonyl complexes and thiolactones derived therefrom

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTChemistry of sulfur-donor ligand ortho-metalated iron carbonyl complexes and thiolactones derived therefromHoward Alper and William G. RootCite this: J. Am. Chem. Soc. 1975, 97, 15, 4251–4257Publication Date (Print):July 1, 1975Publication History Published online1 May 2002Published inissue 1 July 1975https://doi.org/10.1021/ja00848a017RIGHTS & PERMISSIONSArticle Views127Altmetric-Citations33LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (762 KB) Get e-Alerts Get e-Alerts

Crystal and molecular structure of tricarbonyl[(methylsulfidomethyl)phenyl-2-C,S]triphenylphosphinemanganese, an ortho-metalated complex of a sulfur donor ligand

Crystal and molecular structure of tricarbonyl[(methylsulfidomethyl)phenyl-2-C,S]triphenylphosphinemanganese, an ortho-metalated complex of a sulfur donor ligand

Supported transition metal complexes : II. Silica as the support

Liganding groups may be chemically bonded to silica by reaction of the surface silanols with molecules of the type RSiX 3, in which R is an organic group containing a ligand atom and X is a hydrolysable group (eg OC 2H 5). Ligandsilicas, so formed, may be used to prepare transition metal complexes. Alternatively complexes with a ligand containing a SiX 3 group may be prepared and subsequently bonded to the silica surface. The principles are illustrated by the preparation of some phosphorus, nitrogen, sulphur and oxygen donor ligands and ligand-silicas. Carbonyl containing rhodium complexes of these ligands are described.

Complexes of molybdenum(III) with sulphur-donor ligands

Reaction of [Mo2O2Cl2(H2O)6], (I), with ligands L gives complexes [MO2O2(H2O)xLy][L =S-methyl-L-cysteinato hydrochloride (x= 4, y= 2). (II), and 2-aminoethanethiolato hydrochloride (x= 6, y= 2)(III)], [Mo2(OH)2L4][L = 4-mercaptotoluene-3-thiolato. (IV), and 2-aminobenzenethiolato, (V)], [MoL3]2(VI; L =NN-diethyldithiocarbamato). and [Mo2OCIL3](VII; L = 2-hydroxyethanethiolato). l.r., u.v., visible, n.m.r., and e.s.r. spectra and magnetic susceptibilities of the complexes are reported. Structures are proposed. The complexes are bi- or poly-nuclear. With bidentate thiols. sulphur bridges are formed between molybdenum atoms. In reactions with thiols, oxide bridges are readily replaced probably via initial protonation of bridging oxide. The complexes are discussed in the general context of molybdenum chemistry. The tendency to form sulphur-bridged complexes is greater with molybdenum (III) than with molybdenum(V). Sulphur bridges are less labile than oxygen bridges.

Cyclometallation reactions. XV. ortho-Metallation of a sulphur-donor ligand

The reaction between benzyl methyl sulphide and Mn(CH2Ph)(CO)5 affords the ortho-metallated-complex Mn(C6H4CH2SMe)(CO)4. Some other, non- metallated complexes of the sulphur-donor ligand with ruthenium and palladium are described; with rhenium, a complex disproportionation reaction occurs, apparently giving mixed [Re(CO)3(SR)]4 (R = Me, Ph or CH2Ph) complexes.

Desulfurization and ortho-metalation reactions of dimanganese decacarbonyl

Thiobenzophenone, and 4,4′-disubstituted derivatives having moderately electron-donating (methyl, methoxy) or electron-withdrawing (fluoro) groups, react with dimanganese decacarbonyl in refluxing heptane to produce olefins (and a sulfur manganese carbonyl complex) in good yield. 4,4′-Bis(dialkylamino)thiobenzophenones reacted with the metal carbonyl to give sulfur-donor ligand ortho-metalated complexes as the major product and 4,4′-bis(dialkylamino)diphenylmethanes as by-products. A mechanistic scheme is proposed for these reactions.

The carbonyl insertion reaction of sulfur-donor ligand ortho-metalated iron carbonyl complexes

Amines, phosphines, alcohols, and thiocyanate ion are useful reagents for effecting carbonyl insertion of sulfur-donor ligand ortho-metalated iron carbonyl complexes. The apparent intermediate in these reactions has been isolated.

Novel Stereochemical Features of Some Ni(II) Complexes Involving Sulphur Donor Ligands

Novel Stereochemical Features of Some Ni(II) Complexes Involving Sulphur Donor Ligands