Thiolato Ligands Research Articles

Cobalt complexes with pnicogen (phosphine or pyridine) and thiolato ligands. Syntheses, x-ray crystal structures and spectroscopic characterization

Mixed pnicogen and thiolato mononuclear cobalt complexes, Co(SR) 2(PBu n 3) 2 [R = Ph ( 1); R = Stolyl- p ( 2)] and Co(mpo) 2L [L = PBu n 3 ( 3); L = Py ( 4)], have been synthesized and studied spectroscopically. The complexes 1 and 2 are tetrahedral, as determined by magnetic susceptibility studies. The structures of 3 and 4 were determined by X-ray diffraction. The cobalt(II) ions in both 3 and 4 are in a square-pyramidal environment with the two trans-oriented mpo ligands in the basal plane and the pnicogen group in the axial position.

Novel Metal Thiolates: [Co2(SC3H7)5]−, the First Complex with Face‐Sharing MS4 Tetrahedra

A trigonal bipyramid made up of sulfur atoms with two cobalt atoms in the cavity, or two face-sharing CoS4 tetrahedral—both are apt descriptions of the structure of the title anion 1. The CoCo distance is remarkably short (2.491(1) Å), and the isopropyl groups of the three bridging thiolato ligands have a paddle-wheel-type arrangement about a C3 axis. Complex 1 is obtained from cobalt(II) nitrate and sodium propane-2-thiolate and can be isolated as the ammonium salt.

Synthesis of Cubane‐like and Double Cubane‐like Tungsten‐Copper‐Sulfur Clusters from the “Butterfly” Cluster [Cu2S3W(O)(PPh3)3

The denticity of the thiolato ligand decides whether the cubane‐like cluster 1 or the bicubane‐like cluster 2 is obtained in the reaction of copper thiolates with the “butterfly” cluster [Cu2S3W(O)(PPh3)3]. This could also be confirmed by further cluster syntheses. Tungsten–copper–sulfur clusters such as 1 and 2 are of interest, inter alia, as models for the active centers of some enzymes. equation image

Thiolato ligands derived from chiral ferrocenylphosphines: synthesis and structure of the trimeric copper(I) complex [{(R)-(S)-CpFe(.eta.5-C5H3(1-PPh2)(2-CH(CH3)S))}Cu

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThiolato ligands derived from chiral ferrocenylphosphines: synthesis and structure of the trimeric copper(I) complex [{(R)-(S)-CpFe(.eta.5-C5H3(1-PPh2)(2-CH(CH3)S))}Cu]3Antonio Togni, Grety Rihs, and Ruth E. BlumerCite this: Organometallics 1992, 11, 2, 613–621Publication Date (Print):February 1, 1992Publication History Published online1 May 2002Published inissue 1 February 1992https://doi.org/10.1021/om00038a019RIGHTS & PERMISSIONSArticle Views189Altmetric-Citations34LEARN 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 (2 MB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Synthesis, structure determination and immobilization of some dirhodium complexes with chiral binding thiolato ligands. Investigation of their catalytic activity for enantioselective hydrogenation

(−)- cis[Dicarbonyl-μ-chloro-[μ-6,6-dimethylbicyclo[3.1.1]heptane-2-methanethiolato- S:S)]]bis[tris(1,1-dimethylethyl)phosphine]dirhodium ( 5a) and (+)- cis-[dicarbonyl-μ-chloro-[μ-5β-methyl-2α-(1-methyl-ethyl)cyclohexanethiolato- S:S]]bis[tris(1,1-dimethylethyl)phosphine]dirhodium ( 5b) were prepared from [Rh(CO) 2] 2(μ-Cl) 2, P(t-Bu) 3 and the corresponding sulfides (−)- cis-(myrtanethio)trimethylsilane ( 4a) and (+)-(neomenthanethio)trimethylsilane ( 4b). The molecular structures of 5a and 5b were determined by single-crystal X-ray diffraction ( 5a: C222 1, a = 13.749(4), b = 23.509(9), c = 27.271(9) Å, Z = 8, R = 0.0443, R w = 0.0491. 5b: P 1 , a = 16.209(6), b = 14.150(5), c=9.899(3) Å, Z = 2, R = 0.058, R w = 0.094). Complex 5b was found to exist in the crystal as a pair of 1 R,2R,5S- and 1S,2R,5S-epimers. Both chiral complexes have been immobilized by attachment to divinylbenzene-crosslinked polystyrene resins. Application of the chiral dirhodium complexes as catalysts for hydrogenation of methyl α-acetamidocinnamate revealed that while 5b leads to optically active N-acetylphenylalanine methyl ester (up to 50% ee) 5a gives only the racemic product. The immobilization of the complexes proved to improve the enantioselectivity of 5a but decreases the ability of 5b to induce asymmetric reduction.

Reaction of Carbon Monoxide with Iron(II) Thiolates. Preparation and Structure of fac‐[Na(15‐Crown‐5)][Fe(CO)3(SPh)3] and fac‐[K(18‐Crown‐6)][Fe(CO)3(SPh)3

AbstractSolutions of Fe(II) and thiolates (RS‐: Fe2+ > 2; R = alkyl, phenyl) absorb carbon monoxide and ‐ depending on the reaction conditions ‐ several different anionic iron carbonyl derivatives are formed. Two of these complexes, fac‐[Na(15‐crown‐5)][Fe(CO)3(SPh)3] (1) and fac‐[K(18‐crown‐6)][Fe(CO)3(SPh)3] (2) were isolated and their crystal structures determined. (1) Crystallizes in the triclinic space group P1 with a = 11.915(3)Å, b = 12.391(3)Å, c = 14.337(3)Å, α = 65.77(5), β = 116.28(5)°, γ = 105.87(5)°, V = 1720(1)Å3, Z = 2, dcalcd = 1.30 gcm−3; (2) crystallizes in the cubic space group Pa3, with a = 19.609(4)Å, V = 7540(3)Å3, Z = 8, dcalcd = 1.4 gcm−3. Final agreement factors were R = 0.092, Rw = 0.102 (3919 reflections with F>7σ(F)) for (1); and R = 0.069, Rw = 0.050 (1125 reflections with F>4σ(F)) for (2). Both [Fe(CO)3(SPh)3]− anions of 1 and 2 have the same octahedral ligand arrangement with the carbonyl ligands cis to each other and trans with respect to the thiolato ligands. In complex 2 the K+ lies on the crystallographic threefold axis and is therefore exactly equidistant (3.475(2)Å) from the three sulphur atoms; on the contrary in complex 1 in the Na+ is nearer to two of the three sulphur atoms (3.083(6)Å and 3.334(6)Å for the two different Na…S distances). The infrared spectra of the compounds were recorded in a variety of solvents and in the solid state. The Raman of crystalline 2 was also recorded. The failure of the vibrational spectra of crystalline 2 to follow either molecular point group or factor group predictions is explained in terms of an effective vibrational unit ‐ and so, effective factor group ‐ similar to that implicit in a factor group analysis of 1.

Transition metal complexes with sulphur ligands. Part 67. A novel type of reaction: nucleophilic alkylation of thiolato ligands by carbanions via intramolecular electron transfer. Alkylation and reduction of [W(S2C6H4)3] by lithium alkyls

The reaction of [W(S2C6H4)3]1 with LiMe depends on the concentration of the latter and yields either the anionic tungsten(IV) complex [NR4][W(S2C6H4)2(MeSC6H4S)](R = Me, 2a; or Et, 2b) or the anionic tungsten(V) complex [NMe4][W(S2C6H4)3]3b. This novel type of reaction demonstrates the reactive versatility of transition-metal sulphur centres and is of importance for the understanding of trans-methylation reactions catalysed by oxidoreductases with sulphur-co-ordinated transition-metal centres, e.g. CO dehydrogenase. When 1 is treated with LiEt, LiCH2But or LiPh only a reduction of 1 takes place yielding 3b. The reaction of complex 1 with 2 equivalents of LiBun affords the dianionic tungsten(IV) complex [NMe4]2[W(S2C6H4)3]4. The electrophilic alkylation of 4 by 2 equivalents of R3OBF4(RMe or Et) or of 2b by 1 equivalent of Me3OBF4 leads to the doubly alkylated complexes [W(S2C6H4)(RSC6H4S)2](R = Me, 5a; or Et, 5b).

ChemInform Abstract: The Novel Redox Reaction and Thiolato Ligand Transfer Between Cp2Ti(SCMe3)2 and CpCo(CO)2. Preparation and Structure of (CpCo(μ‐SCMe3))2.

Abstract(III), crystallizing in P21/n with Z=4, is the first structurally characterized Co complex of this type.

Synthese und Struktur von Thiolatokomplexen des einwertigen Kupfers: Tetrameres und Octameres [CuSC6H2(i-Pr)3] / Synthesis and Structure of Thiolato Complexes of Monovalent Copper: Tetrameric and Octameric [CuSC6H2(i-Pr)3

[CuSC6H2(i-Pr)3]n = 4 (1), and n = 8 (2) are obtained from CuCO3 · Cu(OH)2 and 2,4,6-tri(isopropyl)thiophenol in a slow reaction, where long reaction times promote the formation of octameric 2.1 crystallizes as colorless platelets, space group C 2/c: a = 3647(2), b = 854.8(6), c = 2061.3(7) pm, β = 105.98(4)°, Ζ = 4. Central unit of the tetrameric complex with the symmetry C2 is a non planar eight-membered Cu–S heterocycle. The four Cu atoms form a rhombus with short edges of 269.7 and 270.1 pm. The bridging SR-ligands are arranged alternatingly above and below the Cu4 rhombus. Octameric 2 crystallies as 2•(H2O)x in the form of orthorhombic yellow blocks, space group Pbcn: a = 2513(1), b = 1975(1), c = 2747(1) pm, Z = 4. The thiolato ligands connect the Cu atoms to form a folded 16-membered Cu–S ring with the symmetry C2. The eight S atoms are arranged at the corners of a cube with the Cu atoms occupying eight of its edges. The Cu–Cu distances are in the range of 267.8 to 304.0 pm. In 1 as well as in 2 the Cu atoms are linearly coordinated with Cu–S distances of 214.7 to 217.9 pm.

The novel redox reaction and thiolato ligand transfer between Cp2Ti(SCMe3)2 and CpCo(CO)2. Preparation and structure of [CpCo(.mu.-SCMe3)

The novel redox reaction and thiolato ligand transfer between Cp2Ti(SCMe3)2 and CpCo(CO)2. Preparation and structure of [CpCo(.mu.-SCMe3)

Synergism in molybdenum iron sulphur cluster compounds. Synthetic, structural, magnetic, cyclic voltammetric evidence and the reaction of dicubane clusters containing [MoFe3S4] unit

Dicubane cluster compounds (Et4N)4[Mo2Fe7S8(SR)12] (2A) (R=Ph,a;o-tolyl,b;m-tolyl,c;p-tolyl,d) were made by reaction of (Et4N)2[Fe4(SR)10] (1) with (Et4N)2MoS4 in MeCN at room temperature. The structure,1Hn.m.r.,57Fe Mossbauer spectrum, magnetic susceptibility and cyclic voltammogram are described. (Et4N)3[Mo2Fe6S8Cl6(SR)3] (3) (R=Ph,a;m-tolyl,b) was obtained from the reaction of (2Aa) or (2Ac) with acetyl chloride in MeCN. This is the first time that compound of structural type (2) is transformed into that of structural type (3) by chemical conversion. Compound (2Aa) crystallizes in the triclinic space group P $$\bar 1$$ with Z=1 and unit cell dimensionsa=12.775(4),b=13.076(3), andc=20.576(4) A; the structure was refined to R=7.7% using 4031 unique data with I>3ϖ(Io). Compound (2Ac) 2THF crystallizes in the monoclinic space group P21/n with Z=2 and unit cell dimensionsa=18.022(2),b=18.375(2) andc=22.254(3) A; the structure was refined to R=6.4% using 5173 unique data with I>3ϖ(Io). Compound (3b) crystallizes in the hexagonal space groupP63/m with Z=2 and unit cell dimensionsa=b=16.827(3) andc=15.951(16) A; the structure was refined to R=4.9% using 1296 unique data with I>3ϖ(Io). Its characteristics are discussed and compared with those of known compounds. The ratios of core volumes S4/M4 are within the 2.34–2.40 range for core oxidation level [MoFe3S4]3+ indicating that distortion of the cubane core is a general phenomenon. Different thiolato ligands induce significant changes of structural parameters only at the Fe(SR)6 region for compound (2A) while terminal chlorides induce changes over the whole molecule of (3b) with the latter structure more comparable to [Mo2Fe6S8(SPh)9]5− (3f) with [MoFe3S4]2+ core than to [Mo2Fe6S8(SPh)9]3− (3d). The isotropic shifts of (2A) originate mainly from π-contact interaction. Both1H n.m.r. spectra and magnetic susceptibility measurements indicate practically no magnetic interaction among the three magnetic centres,i.e. a Fe(SR)6 bridge and two [MoFe3S4(SR)3] units. CV studies showed that the reduction of cubane unit having aromatic thiolates is easier than that having aliphatic thiolates as the aliphatic group is electron-donating. In addition, the very similar differences of Ep,c for first and second cubane units in compounds (2A) and in (3d) and (3e) imply that the effect of the first reduced unit [MoFe3S4]2+ upon the second unit [MoFe3S4]3+ is very similar in the two types of dicubane cluster compounds. Synergism in Mo−Fe−S cluster compounds is thus proposed to play an important role in their structural correlation with reactivities and must function in nitrogenase.

ChemInform Abstract: Coordination Chemistry of Sterically Hindered Thiolate Ligands. Preparation and Structural Characterization of the Oligomeric Homoleptic Complexes (Cu(SC6H4‐o‐SiMe3))12 and ((Ag(SC6H4‐o‐SiMe3))4)2 and a Comparison to the Structure of the Mononuclear Species (Et4N)2(Cd(SC6H4‐o‐SiMe3)4).

AbstractThe thiolato ligand is prepared by a known method.

The X-ray crystal structure of di-η 5-cyclopentadienylthiophenolatoamminemolybdenum(IV) hexafluorophosphate solvate [Mo(η 5-C 5H 5) 2(NH 3)(SC 6H 5)][PF 6] · (CH 32CO

Crystals of [Mo(η 5-C 5H 5) 2(NH 3)(SC 6H 5)][PF 6] · (CH 3) 2CO solvate are monoclinic, space group P2 1/ n, a 9.777(1), b 11.6343(2), c 19.656(4) Å, β 93.60(1)°, V 2231-46 Å 3, Z  D c 1.617 g cm −3, μ(Mo- K α) 7.21 cm −1. The structure was solved by Patterson and difference Fourier electron density synthesis and refined to R ( F)  0.047 and R w( F)  0.057 for 3293 observed reflections. The molybdenum atom has the usual distorted tetrahedral geometry comprising the two MoCp (Cp  η 5-C 5H 5) ring normals (MoCp 1.988(13), 1.989(15) Å), one Mo-NH 3 (MoN 2.226(12) Å), and one MoSc 6H 5 (MoS 2.465(5) Å). Extended HMO and steric energy calculations were made in order to account for the geometry adopted by the thiolato ligand in this complex.

Transition metal promoted reactions: XVI. Activation of CS bonds in complexed thiolato ligands. Reduction of the CS bond in Cp 2Ni 2(μ-SR) 2

The carbon-sulfur bond in Cp 2Ni 2(μ-SR) 2 is reductively cleaved by treatment with lithium aluminium hydride to give the corresponding carbonhydrogen bond. Preliminary examination of the reaction mechanism is described.

ChemInform Abstract: Axial Ligand Replacement Reactions in Tetrakis(μ‐phosphato)diplatinum(III) Complexes: Coordination of Amine, Thioether, and Thiolate Functionalities.

AbstractThe labile water molecules in the diplatinum(III) complex (Ia) are sequentially replaced by halide, amine, thioether, and thiolato ligands.

STABILIZATION OF MONOOXOMOLYBDENUM(V) COMPLEXES [MoO(SR)4]1− USING PEPTIDE THIOLATO AND BULKY AROMATIC THIOLATO LIGANDS

Abstract Mononuclear monooxomolybdenum(V) peptide complexes having hydrophobic amino acid residues adjacent to Cys residue, [MoO(Z-cys-Val-OMe)4]1− and [MoO(Z-cys-Pro-Leu-cys-OMe)2]1−, exhibit large A|| values (54.2×10−4 cm−1 and 56.6×10−4 cm−1, respectively) in the EPR spectra. Other monooxomolybdenum(V) complexes having bulky thiolato ligands, [NEt4][MoO(tmbt)4] (tmbt = 2,4,6-trimethylbenzenethiolato) and [NEt4][MoO(tipbt)4] (tipbt = 2,4,6-triisopropylbenzenethiolato), have been prepared. These have a covalent Mo=O bond as evidenced by the EPR (large A|| of 57.6×10−4 cm−1), and high v(Mo–O) (944 cm−1) from Raman spectroscopy on the latter complex). Electrochemical reduction of these complexes results in removal of the oxo ligand.

SYNTHESIS AND REDOX BEHAVIOR OF [Mo(2,4,6-TRIALKYLBENZENETHIOLATO)4]. UNIQUE REDOX PROPERTIES OF TETRA-COORDINATED Mo(IV) COMPLEXES WITH BULKY THIOLATES

Abstract Two new molybdenum(IV) complexes having bulky thiolato ligands, [Mo(2,4,6-trimethylbenzenethiolato)4] and [Mo(2,4,6-triisopropylbenzenethiolato)4], were synthesized. These complexes show paramagnetic properties due to a nearly tetrahedral coordination and exhibit the quasi-reversible redox couples of Mo(V)/Mo(IV) at −0.07 V and +0.47 V vs. SCE, respectively in 1,2-dimethoxyethane. The two bulky isopropyl groups at o-position prevent π-interaction between Mo(IV) and sulfur, providing an ionic character at the Mo–S bond and stabilizing Mo(IV) state against oxidation.

Models for coordination site of cytochrome P-450, characterization of hemin-thiolato complexes with S, O, and N donor ligands by electronic absorption

Bisthiolato-hemin complexes exhibiting “two split Soret bands” at 370 and 460 nm, classified into “hyperporphyrin spectrum” was prepared with naturally occurring porphyrins (Fe(III)protoporphyrin IX and its dimethyl ester), thioglycolate esters, and tetramethylammonium hydroxide in organic solvents. The structure of the complexes was characterized by electronic absorption and electron spin resonance (ESR) spectrometries. These complexes were stable under air at room temperature, their apparent half-lives being about 30 min monitored by the intensities of the two Soret bands. Thus the bisthiolato-hemin' complex containing thioglycolate ester was shown to be a model for the cytochrome P450(P450)-thiolato binding complex. Ligand exchange reactions of the bisthiolato-hemin complex with imidazole or methanol indicated that the intermediate species are stabilized as thiolato-hemin-imidazole or -methanol complexes. The latter intermediate complex was suggested to be a good model for low-spin ferric P450 as characterized by distinct β- and α-bands at 530 and 560 nm, respectively, as well as a single Soret peak at ~410 nm. The result of the analysis on ESR g values and crystal field parameters for the bisthiolatohemin, thiolato-hemin-imidazole, and thiolato-hemin-oxygen ligand complexes comparing with those for P450 itself and the ligand binding complexes revealed that the sixth ligand trans to the fifth thiolato ligand of the low-spin ferric P450 can be an oxygen atom of water molecule.

Synthesis of polymer-bound nitridomolybdenum(VI) complexes as model polymer complexes of nitrogenase: effect of polymer environment in the Hydrolytic formation of ammonia

Polymer-bound nitridomolybdenum(VI) complexes, MoNCl 3(polystyrene-bound bipyridyl) (I), MoNCl 2(bpy)(polystyrene-bound benzylthiolato) (II), and MoNCl (S-t-Bu)(bpy)(polystyrene-bound benzylthiolato) (III), were synthesized by the reaction of MoNCl 3(CH 3CN) x or MoNCl 3(bpy) with polystyrene-bound bipyridyl or benzylthiol. The polymer-bound nitridomolybdenum complexes were characterized by photo-acoustic and resonance Raman spectra. Hydrolysis or hydrolytic reduction of the nitridomolybdenum(VI) complexes resulted in the formation of ammonia in the following order of yield: III & II & I. Coordination of the polymer thiolato ligands is thus important in enhancing reductive cleavage of the nitridomolybdenum bond.

Metal-induced cleavage of carbon-sulfur bonds in thiolato ligands. Thermolysis of HOs3(CO)10(.mu.-SC6H5) under carbon monoxide pressure. The synthesis and crystal and molecular structures of Os4(CO)13(.mu.3-S) and Os5(CO)15(.mu.4-S)

Etude des pyrolyses a 150°C sous pression de 200 et 1800 psi. A 200 psi, il y a formation de Os 4 (CO) 13 (μ 3 -S) (II) Os 5 (CO) 15 (μ 4 -S) (III), et de Os 3 (CO) 9 (μ 3 -S) 2 (IV) et Os 3 (CO) 12 . Etude RX de II et III