Sulfido Complexes Research Articles

Synthesis and Reactivity Aspects of the Bis(dithiolene) Chalcogenide Series [WIVQ(S2C2R2)2]2-(Q = O, S, Se)

An improved synthetic route to the previously reported dicarbonyl complexes [W(CO)2(S2C2R2)2] (R = Ph (1), Me (2)) has been developed via the thermal reaction of [W(CO)3(MeCN)3] and [Ni(S2C2R2)2] in dichloromethane (60−70%). Complexes 1 and 2 are shown to be useful synthetic precursors by means of carbonyl ligand displacement. Reactions of 1 with Et4NOH, Na2S, and Li2Se afford the previously unknown bis(dithiolene) series [WIVQ(S2C2Ph2)2]2- (Q = O (3), S (6), Se (7), 65−76%). Complex 2 and Et4NOH give [WIVO(S2C2Me2)2]2- (5, 68%). Members of the series manifest absorption spectra that are strongly dependent on Q and redox potentials for WIVQ/WVQ couples that are independent of Q. Reaction of 3 and 5 with MeI or EtI results in mono-S-alkylation as shown by the 1H NMR spectra of [WO(EtS2C2R2)(S2C2R2)]1-, which indicate a single stereoisomer with a diastereotopic methylene group. S-alkylation of 3 was further confirmed by the structure of the reaction product with MeI, [WO(MeS2C2Ph2)(S2C2Ph2)]1- (8, 65%), which reveals the exo stereoisomer with a pyramidal sulfur atom whose methyl carbon atom is displaced 1.27 Å from the chelate ring plane. Treatment of 3 with hard alkylating agents caused oxidation to [WVO(S2C2Ph2)2]-, independently prepared by reaction of 3 with iodine (78%). Sulfido complex 6 with soft alkylating agents such as MeI gave mixtures. Reaction of 6 with C7H7+ resulted in electron transfer rather than alkylation and the formation of binuclear [WV2(μ-S)2(S2C2Ph2)4]2- (11, 53%). No alkylated species were isolated from selenido complex 7; [W(S2C2Ph2)3] (13) was identified as a reaction product. Electrochemical data and X-ray structural results for 1, 2, 13 (trigonal prismatic), Et4N+ salts of 3, 5, 6 (square pyramidal), 8 (distorted square pyramidal), and 11 (distorted octahedral), and (PhCH2NEt3)[W(S2C2Ph2)3] (distorted trigonal prismatic) are presented.

Formation of Novel Tetrasulfido Tin Complexes and Their Ability To Catalyze the Cyclotrimerization of Aryl Isocyanates

Unusual cyclic tin tetrasulfido complexes {(CyNC(R)NCy)[N(SiMe3)2]}SnS4 (Cy = cyclohexyl; R = Me (3), tBu (4)) were prepared by the reaction of elemental sulfur with newly reported divalent tin starting materials [CyNC(R)NCy]Sn[N(SiMe3)2] (R = Me (1), tBu (2)). Compounds 3 and 4 were further converted to dimeric bridging sulfido complexes, {(CyNC(R)NCy)[N(SiMe3)2]Sn(μ-S)}2 (R = Me (5), tBu (6)), which can also be derived from the oxidative addition of sulfur atom sources (e.g., propylene sulfide) to 1 and 2, respectively. Single-crystal X-ray diffraction studies of 2, 4, and 6 are presented. Compounds 3 and 4 are outstanding catalysts for the cyclotrimerization of aryl isocyanates to perhydro-1,3,5-triazine-2,4,6-triones (isocyanurates) at room temperature. The results of a single-crystal X-ray analysis of triphenylisocyanurate (7) are also reported.

Synthesis and Structural Characterization of Novel Terminal and Bridging Re(V)-Sulfido Complexes.

The new μ-sulfido complex of rhenium(V) shown was one of the new complexes prepared and characterized, along with a mononuclear rhenium(V) complex with one coordinated PPh3.

Evidence for the Existence of a Late-Metal Terminal Sulfido Complex

The transition-metal-sulfur bond is an important linkage in both biological systems1 and industrial catalysts.2 Nickel sulfides, in particular, are key components of natural hydrogenases3 and are active promoters in current hydrotreating catalysts.2 Understanding the nature of the metal-sulfur linkages at active sites can offer insight on ways to improve catalysis and provide a better understanding of cluster formation and cluster interconversion reactions in general. Scheme 1 shows three possible binding modes of a sulfur atom to supported nickel. While numerous examples of binding modes A4 and B5 can be found throughout the literature, there exists no sound evidence for a terminal sulfido complex such as C in the solution phase.6 Additionally, there have been only a few cases for the group 9 and 10 metals where the intermediacy of a terminal sulfido complex has been postulated,7 and there has been no experimental evidence to support the existence of such a species. Terminal sulfido complexes of the earlier transition-metals are well-known, and display a wide range of reactivity.8 Late-metal analogues might then be anticipated to afford similarly rich chemistry. Raney nickel, and homogeneous nickel complexes,9 have been found to desulfurize a variety of organosulfur substrates. The fate of the sulfur atom in these reactions is usually nickel sulfide, thereby preventing catalysis under traditional laboratory conditions. A number of recent reports from our group,10 however, indicate that sulfur can be extracted from organic compounds without the formation of nickel sulfide. These results prompted us to further explore the mechanism of these unique desulfurizations, and to systematically investigate the intermediacy of the three possible binding modes of a sulfur atom to nickel (Scheme 1). In these efforts we have found kinetic and structural evidence that support the chemical feasibility of binding mode C, namely a terminal sulfido complex at nickel. Initial studies were directed toward finding an efficient way to prepare a nickel sulfido complex. Bergman has reported routes to transient [Cp2TidS] and [Cp2ZrdS] using Cp2Ti(SH)H and Cp2Zr(SH)I, respectively. The synthetic strategy that we found to be successful with nickel was based on two very different but related findings. It was discovered by Bergman and co-workers that thermolysis of Cp*2Zr(OH)(Ph) led to the loss of benzene and formation of the terminal oxo complex, which was subsequently trapped by a variety of substrates.12,13 Additionally, Osakada and co-workers found that thermolysis of trans-Ni(Ar)(SH)(PEt3)2 (Ar ) aryl ligand) led to decomposition of the metal with formation of Ar-H and SdPEt3. Curiously, no Ar-SH was formed.14 We wondered whether the loss of arene in this instance was concomitant with the formation of a transient terminal sulfido complex, mimicking the zirconium-oxo chemistry. We therefore prepared a nickel complex containing chelating phosphines and cis-(Ar)(SH) groups to examine if elimination of arene would readily occur. Chelating phosphines were used since recent reports have shown that [L2M(μ-S)]2 complexes (where L2 is a chelating ligand) are thermally quite stable.10b,15 Li2Ni(SH)(Ph) (1a and 1b) [L2 ) dippe (1,2-bis(diisopropylphosphino)ethane) (1a) and dcpe (1,2-bis(dicyclohexylphosphino)ethane) (1b)] were prepared and their thermolysis behavior was studied in solution. Nickel thiols of type 1 were synthesized by the addition of NaSH to L2Ni(Cl)(Ph). It was found that mild heating of 1 in THF solutions led to loss of benzene (1 equiv observed by 1H NMR spectroscopy) and production of the bridged sulfido dimers 2 in quantitative yields by NMR spectroscopy (eq 1). Complex

Synthesis, Structures, and Oxo Transfer Reactivity of Bis(dithiolene)tungsten(IV,VI) Complexes Related to the Active Sites of Tungstoenzymes

A series of bis(dithiolene)tungsten(IV,VI) complexes derived from benzene-1,2-dithiolate (bdt) has been prepared as an synthetic approach to pterin dithiolene-bound active sites of tungstoenzymes, one example of which, a archaeal oxidoreductase, has been established crystallographically (Chan et al. Science 1995, 267, 1463). With [WIVO(bdt)2]2- (2) as the starting compound, silylation with RR‘2SiCl afforded [WIV(bdt)2(OSiRR‘2)]1- (4). Oxidation of 4 with Me3NO gave [WVIO(bdt)2(OSiRR‘2)]1- (5), also accessible by silylation of [WVIO2(bdt)2]2- (3). Reaction of 3 or 5 with Me3SiCl resulted in [WVIO(bdt)2Cl]1- (6), from which the unstable species [WVIO(bdt)2L]1- (L = ButO-, PhS-) were generated in solution. Reductive oxo transfer of 6 with L‘ = P(OEt)3 or ButNC/P(OEt)3 gave [WIV(bdt)2L‘2] (8 and 9). Sulfido complex [WVIS(bdt)2(OSiRR‘2)]1- (12) was obtained in the reaction systems 4/(PhCH2S)2S and 5/(Me3Si)2S. Structures of [WO(SPh)4]1- and [W(bdt)3]2- and eight complexes of types 4−6, 8, 9, and 12 were determined by X-ray crystallography. Complexes 4 and 5 are tungsten analogues of the desoxo Mo(IV) and monooxo Mo(VI) states of Rhodobacter sphaeroides DMSO reductase. Six types of reactivity, including oxygen atom transfer, are recognized by the synthesis and interconversion of the set of complexes. The potential biological relevance of these complexes to the structure and function of active sites in two families of tungstoenzymes is considered (RR‘2 = Me3 (4); ButMe2 (4 and 5), ButPh2 (4, 5, and 12)).

Cycloaddition and Nucleophilic Substitution Reactions of the Monomeric Titanocene Sulfido Complex (η5-C5Me5)2(C5H5N)TiS

The titanocene sulfido complex Cp*2(py)TiS (1, py = pyridine) reacts reversibly with terminal alkynes to give the thiametallacyclobutenes Cp*2Ti(SC(R)CH) (R = H (2), Ph (3), Tol (4), TMS (5)). Complex 1 also reacts with alkyl halides to give products derived from formal 1,2-addition across the titanium−sulfur bond. Treatment of 1 with allyl halides results in the formation of Cp*2Ti(X)SCH2CHCH2 (X = Cl (10), F (16), Br (17), I (18)). Reaction of 1 with alkyl-substituted allyl chlorides showed that displacement of the halide anion occurs with SN2‘ regiochemistry. A kinetic study of the conversion of 1 to 10 is consistent with a mechanism in which pyridine dissociation from the metal center precedes reaction of allyl chloride with the Cp*2TiS fragment. The SN2‘ regiochemistry of the reaction is explained by postulating coordination of the halogen atom to the metal center in the reaction transition state. Complex 1 also reacts with allyl tosylate, but labeling experiments show (in contrast to the allyl chloride reaction) that substitution of the tosylate functionality occurs via a SN2 pathway. Heterocycles formed from the reaction of 1 with α,β-unsaturated aldehydes were also isolated and characterized.

Titanium(II), -(III), and -(IV) Complexes Supported by Benzamidinate Ligands

The synthesis and reactivity of a wide range of titanium benzamidinates is described. Addition of 0.5 equiv of Me2Mg to the dichloride L2TiCl2 (L = PhC(NSiMe3)2) in Et2O yields the chloro−alkyl derivative L2Ti(Me)Cl in good yield. The addition of 2 equiv of PhCH2MgCl to the dichloride affords thermally sensitive L2Ti(CH2Ph)2 in moderate yield. Likewise, addition of 1 equiv of Me2Mg results in the clean formation of the dimethyl L2TiMe2. The dimethyl reacts with tert-butylamine in refluxing benzene to form the five-coordinate imido L2TiNCMe3, for which crystallographic data is presented. The imido reacts with acetone in C6D6 to form the bridging oxo derivative L2Ti(μ-O)2TiL[η1-NC(Ph)N(SiMe3)2]. Overnight reduction of the dichloride with 1% Na/Hg amalgam in tetrahydrofuran (THF) forms the Ti(III) derivative L2TiCl(THF), which is crystallized from hexanes in moderate yield. Carrying out the analogous reduction in toluene yields the base-free Ti(III) chloride, L2TiCl, for which crystallographic data is presented. Allowing the reaction (in toluene) to proceed for an additional 48 h results in further reduction and the formation of the end-on bound dinitrogen complex (L2Ti)2(μ-N2), which is isolated as dark blue crystals from hexanes in moderate yield. Reduction of L2Ti(Me)Cl with 1% Na/Hg amalgam in THF forms the Ti(III) methyl derivative which is isolated as the five-coordinate THF-free product L2TiMe upon evacuation and crystallization from hexamethyldisiloxane (HMDSO). The related Ti(III) alkyl L2TiCH2SiMe3 is readily prepared by reaction of LiCH2SiMe3 with L2TiCl in toluene. Carrying out the 1% Na/Hg amalgam reduction of the dichloride in the presence of CO results in the formation of the Ti(III) bridging-oxo species (L2Ti)2(μ-O), which is isolated in low yield. CO as the sole oxygen source is confirmed by the use of C18O, which yielded only labeled product. Analogous reduction in the presence of N,N,N‘,N‘-tetramethylethylenediamine (TMEDA) results in the C−N bond cleavage of an amidinate ligand and the cyclometalation of TMEDA. Two products, L2TiNSiMe3 and LTi[η2-Me3SiNC(H)Ph][η3-CH2N(Me)CH2CH2NMe2], are isolated in good yields by fractional crystallization from hexanes. The dinitrogen complex, (L2Ti)2(μ-N2), reacts with pyridine (Py) and 2,6-dimethylphenyl isocyanide (XylylNC) to form base adducts [L2Ti(Py)]2(μ-N2) and [L2Ti(CNXylyl)]2(μ-N2) without loss of the dinitrogen ligand. Crystallographic data for the Py adduct is presented. Oxidation reactions of (L2Ti)2(μ-N2) with a variety of oxygen and sulfur sources is reported. Reaction with dry O2 in the presence of pyridine gives the seven-coordinate peroxo complex L2Ti(η2-O2)Py. The related reaction with excess S8 yields the dark-green persulfido derivative L2Ti(η2-S2), for which crystallographic data is presented. The persulfido reacts overnight with Hg in toluene solution to give the bimetallic sulfido complex L2Ti(μ-S)2TiL[η1-NC(Ph)N(SiMe3)2], which is formed following a silyl-group migration. The analogous oxygen-containing product is best prepared by the reaction of powdered (L2Ti)(μ-N2) with dry O2. In the presence of excess pyridine, L2Ti(η2-S2) reacts with Hg to yield the terminal sulfido L2Ti(S)Py. The crystallographically characterized terminal-oxo derivative L2Ti(O)OPy is prepared by reaction of (L2Ti)(μ-N2) with an excess of pyridine N-oxide in toluene−pyridine.

Synthesis and structural characterization of [TpBut2]GaS: a terminal gallium sulfido complex in a system for which the indium counterpart is a tetrasulfido derivative, [TpBut2]In(η2-S4)

The synthesis of the terminal gallium sulfido complex [TpBut2]GaS via the reaction of monovalent [TpBut2]Ga with elemental sulfur provides a striking contrast with the formation of the tetrasulfido derivative [TpBut2]In(η2-S4) in the indium system; such an observation provides a strong indication that gallium exhibits a greater tendency to partake in multiple bonding than does indium.

Bridge to terminal migration and ring closure in a dimolybdenum metallacyclopentadiene complex

The dinuclear complex [Mo2(O)(µ-O)(µ-C4Ph4)(η-C5H5)2] 2a reacted with PhNCO in refluxing toluene to give [Mo2(O)(µ-NPh)(µ-C4Ph4)(η-C5H5)2] 3a. A crystal structure determination of the η-C5H4Me analogue 3b revealed that the bridging C4Ph4 ligand displays an unprecedented bonding mode in which one terminus bridges the two metal atoms whereas the other is bonded to only one molybdenum in the manner of a terminal alkylidene. Owing to the similarity of the 13C NMR spectra of 2a and 3a, we now propose that this bonding mode is also present in the former, and that the ligand rearrangement occurs during the air oxidation of the metallacyclopentadiene complex [Mo2(CO)(µ-C4Ph4)(η-C5H5)2] 1 to form 2a. The reaction of 2a with PriSH afforded an analogous sulfido complex, [Mo2(S)(µ-O)(µ-C4Ph4)(η-C5H5)2] 4a. A second product of this reaction was identical to that formed by treatment of 2 with elemental sulfur and had the formula [Mo2(O)(µ-O)(µ-S)(η-C4Ph4)(η-C5H5)2] 5a. The crystal structure of the analogous complex [Mo2(O)(µ-O)(µ-S)(η-C4tol4)(η-C5H4Me)2] 5d was determined, and confirmed that the C4R4 ligand had closed up into an η4-cyclobutadiene ring. This sequence of reactions therefore represents the gradual migration of the bridging metallacyclopentadiene unit partially (in 2 or 3) or wholly (in 5) onto one molybdenum atom, a process believed to be sterically driven.

A New Entry into Molybdenum/Tungsten Sulfur Chemistry: Synthesis and Reactions of Mononuclear Sulfido Complexes of Pentamethylcyclopentadienyl−Molybdenum(VI) and −Tungsten(VI)

A series of mononuclear thio complexes of pentamethylcyclopentadienyl−molybdenum(VI) and −tungsten(VI) have been synthesized via C−S bond-cleaving reactions of thiolates. Use of Li2S2 for sulfurization of Cp*MoCl4 resulted in the known dinuclear complex, anti-Cp*2Mo2(S)2(μ-S)2 (1), while the analogous reaction of Cp*WCl4 gave rise to anti-Cp*2W2(S)2(μ-S)2 (2) and (PPh4)[Cp*W(S)3] (3), the latter of which was isolated after the subsequent cation exchange reaction with PPh4Br. In contrast, the reaction of Cp*WCl4 with Li2edt (edt = SCH2CH2S) followed by treatment with PPh4Br generated 3 as the sole isolable product in high yield. A similar reaction between Cp*WCl4 and LiStBu afforded Cp*W(S)2(StBu) (6), which turned out to be thermally unstable in solution and gradually degraded to 2. In these reactions of Cp*WCl4 with lithium thiolates, a facile C−S bond cleavage took place and the tungsten atom was oxidized from W(V) to W(VI). On the other hand, the Mo(IV) thiolate complexes, Cp*Mo(StBu)3 (4) and (PPh4)[C...

Synthesis of (Pentamethylcyclopentadienyl)tantalum Sulfido Complexes via C−S Bond Cleavage of Triphenylmethanethiolate and Formation of a Novel Trithioborato Ligand

Treatment of Cp*TaCl4 with triphenylmethanethiol via C−S bond cleavage gave rise to Cp*TaCl(S)(SCPh3) (1), which was treated with LiSR, Li2S, and NaBH4 to afford Cp*TaS(SR)(SCPh3) (R = CPh3 (2), CMe3 (3)), [Cp*Ta(S)3Li2(THF)2]2 (4), and Cp*3Ta3(S)3(S3BH) (5), respectively. The crystal structures of 1 and 5 were determined by X-ray diffraction.

Structural Studies on Indium and Tin Thiobenzoates

AbstractIndium(III) and tin(IV) thiocarboxylates were prepared and characterized on the basis of their IR,13C‐ and19Sn‐NMR data. Indium tris(thiobenzoate) (1) decomposes into a sulfido complex In (S)[S(O)CPh] (2a). The corresponding tris(thioacetate) In[S(O)CMe]3is thermally too unstable to be isolated. The anionic tetrakis complex [Et3NH]{In[S(O)CPh]4} (3) was characterized by X‐ray crystallography which revealed a distorted tetrahedral coordination at the In atom. X‐ray diffraction analysis of the complexes BuSn[S(O)CPh]3(4) and Cl2Sn[S(O)CPh]2(7) showed distorted tetrahedral andcis‐octahedral structures, respectively.

Multiple Bonds between Sn and S: Synthesis and Structural Characterization of (CyNC(tBu)NCy)2SnS and [(CyNC(Me)NCy)2Sn(μ-S)]2

Two new sulfido complexes of tin have been prepared by the reaction of styrene sulfide with novel tin(II) amidinate complexes. These compounds exhibit two very different bonding modes for the sulfi...

Novel butterfly tungsten-osmium carbido cluster Complexes from the reaction of Os3(CO)10(NCME)2 CPW(CO)3(CH2SMe)

Condensation of be triosmium acetonitrile complex Os3(CO)10(NCMe)2 with the sulfido complex CpW(CO)3(CH2SMe) in refluxing THF solution produced three sulfur-containing compounds Os3(C0)10)(µ-H)(µ-SMe) (1), Os3(CO)11 [S(Me)CH2W(CO)3Cp] (2) and CpWOs3(CO)12(µ-CH2)(µ-SMe) (3). Clusters 2 and 3 were products involving a 1:1 combination of starting materials and were characterized by X-ray diffraction studies. Crystals of 2 belongs to monoclinic space group P 21 /c witha=8.418(2),b = 11.912(2),c = 28.288 Å,β=97.64(2)°,Z=4;R F=0.044,R W,=0.044. Crystal dara far 3: space group P 21/e,a 18.156(4).b=9.255(6),c = 15.347(4) Å.β = 103.49(2)°,Z = 4;R F -=0.047,R W = 0.045. Upon thermolysis in toluene, the methylene cluster 3 released CO and induced C-H bond activation to afford two tetrametallic carbido clusters with formula CPWOS3(CO)9(µ4-C)(µ-H)2(µ-SMe) (4) and CPWOs3(CO)11(µ4-C)(µ-SMe) (5) as the principle products. The first complex possesses a butterfly framework encapsulating a µ4-C ligmd and a µ-SMe ligand linking a W-Os edge, whereas the second product adopts a puckered, cyclic arrangement of WOs3 metal atoms with µ-SMe ligand located on a nonbonding Os-Os vector. Complex4 crystallizes in monoclinic space group P 21 /c witha=15.633(4) Å,b = 8.699 (3) Å,c=15.422(4) Å,β=93.12(2)=°, Z=4,R=0.036,R W =0.034 for 2780 observed reflections. Crystal data for5: space groupP nma,a=14.542(3),b=13.710(6),c=11.758(3) Å.Z=4,R F =0.038,R W = 0.037 for 1826 observed reflections. A variable temperature1H NMR study was also presented to demonstrate the solution fluxionality of5.

Reactions of Di- and Polynuclear Complexes. 14. Synthesis of Permethylated-Cyclopentadienyl Chalcogeno-Bridged Compounds: A Route to the Stable Thiolatosulfidocarbonyldimolybdenum(III) Complex [Cp*2Mo2(CO)2(.mu.-SMe)2(.mu.-S)]. Crystal Structure Determination of [Cp*2Mo2(CO)2(.mu.-SMe)2(.mu.-SH)][BF4

The new diamagnetic carbonyl-containing sulfido complex [Cp*2Mo2(CO)2 (μ-SMe)2(μ-S)] (8) has been obtained by the thermal reaction of the pentamethylcyclopentadienyl compound [Cp*2Mo2(CO)4] (1) with MeSSMe; the other predominant product of the reaction, [Cp*2Mo2(CO)4(μ-SMe)2] (3), results from the oxidative addition of dimethyl disulfide across the Mo2 center. Monitoring this thermal reaction by IR spectroscopy indicated that 8 arises from decarbonylative dimerization of [Cp*Mo(CO)3(SMe)] (2). Reactions with other dialkyl and diaryl chalcogenides, REER (ER = SPh, SeMe), and with thiol (HSBz) and selenol (HSePh) led only to the formation of tetracarbonyl chalcogenato-bridged derivatives [Cp*2Mo2(CO)4 (μ-ER)2] (ER = SPh (4), SBz (5), SeMe (6), SePh (7)). A thermolysis study showed the degradation of 3 to [Cp*2Mo2(μ-SMe)4] (12) via [Cp*2Mo2(CO)2(μ-SMe)2] (9); 8 was decarbonylated directly to 12. Investigation of the reaction between 8 and electrophilic reagents showed that dinuclear molybdenum(III) complexes [Cp2*Mo2(CO)2(μ-SMe)2(μ-SH)]X [X = BF4 (16), Cl (17), F(18)] were formed stereospecifically as the cis isomers. 16 has been structurally characterized by X-ray diffraction. Crystals of 16 are orthorhombic, space group Pcab, a = 15.655(5) A, b = 16.173(3) A, c = 23.662(5) A, and Z = 8. The complex cation has approximate C2v symmetry and the Mo-Mo bond length is 2.772(2) A. Complex 3 was readily oxidized by Ag[BF4] to yield the dicationic product [Cp*2Mo2(CO)4(μ-SMe)2][BF4]2 (21). All new thiolato-bridged complexes have been characterized by spectroscopic analyses. © 1995, American Chemical Society. All rights reserved.

Late Transition-Metal Sulfido Complexes: Reactivity Studies and Mechanistic Analysis of Their Conversion into Metal-Sulfur Cubane Complexes

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTLate Transition-Metal Sulfido Complexes: Reactivity Studies and Mechanistic Analysis of Their Conversion into Metal-Sulfur Cubane ComplexesDaniel A. Dobbs and Robert G. BergmanCite this: Inorg. Chem. 1994, 33, 23, 5329–5336Publication Date (Print):November 1, 1994Publication History Published online1 May 2002Published inissue 1 November 1994https://doi.org/10.1021/ic00101a027RIGHTS & PERMISSIONSArticle Views230Altmetric-Citations53LEARN 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 and Reaction Chemistry of New, High-Oxidation-State Ruthenium and Osmium Sulfido Complexes

Synthesis and Reaction Chemistry of New, High-Oxidation-State Ruthenium and Osmium Sulfido Complexes

Synthesis of sulfido and oxo complexes of technetium(V) and rhenium(V) containing dithiolato and hydrotris(1-pyrazolyl)borato ligands. Crystal structures of dimeric bis(.mu.-ethane-1,2-dithiolato)bis(ethene-1,2-dithiolato)technetium(IV) and [hydrotris(1-pyrazolyl)borato](ethane-1,2-dithiolato)oxorhenium(V)

The new technetium(V)sulfido complexes [TcS(edt)[sub 2]][sup [minus]] (1) and [TcSCl[sub 2](HB(pz)[sub 3])] (3) have been prepared and characterized. These species constitute the first examples of technetium complexes containing a terminal Tc[double bond]S bond. Complex 1 was obtained from [TcCl[sub 6]][sup 2[minus]] by reaction with ethane-1,2-dithiol (H[sub 2]edt), while 3 was formed from [TcOCl[sub 2](HB(pz)[sub 3])] by atom transfer from B[sub 2]S[sub 3]. The rhenium analog of complex 3, [ReSCl[sub 2](HB(pz)[sub 3])] (4), has been also prepared. In the synthesis of 1, the dimeric Tc(IV) complex [Tc[sub 2](edt)[sub 2](e[double bond]dt)[sub 2]] (2) (e[double bond]dt = ethene-1,2-dithiolato) was isolated by precipitation. 2 represents the first example of a technetium complex containing two terminal dithiolene and two bridged dithiolato ligands. The conversion of ethane-1,2-dithiolato to ethene-1,2-dithiolato in the reaction of preparation of 1 and 2 seems to play a key role in the formation of the [Tc[double bond]S][sup 3+] core. The X-ray crystal structure of complex 2 showed the Tc atom in a trigonal prismatic array. 2 crystallizes in the triclinic space group P[bar 1]. The reactions of various monothiols and dithiols with [MCl[sub 6]][sup 2[minus]] and [MOCl[sub 2](HB(pz)[sub 3])] (M = Tc, Re) are also discussed. The X-ray crystal structure of onemore » product of these reactions, namely the complex [ReO(edt)(HB(pz)[sub 3])] (5), has been determined. 5 was monomeric with the Re atom in a distorted octahedral environment. It crystallizes in the monoclinic space group P2[sub 1]/c. 31 refs., 3 figs., 5 tabs.« less

Mononuclear mixed oxosulfidomolybdate(VI) complexes with aminodicarboxylic ligands. Synthesis and spectroscopic characterization by multinulcear magnetic resonance spectroscopy

Addition of B 2S 3 to a methanolic solution of the Mo VIO 3L 2− complex (L= N, N-bis(ethanoic acid)-1-amino-2- methylthio-ethane) results in the formation of two different monomeric oxosulfidomolybdate(VI) complexes, [MoO 2SL] 2− and [MoOS 2L] 2− as indicated by 1H, 13C, 17O and 95Mo NMR spectroscopy and by the reaction of these two sulfurated species with triphenylphosphine. The temperature dependences of the 1H NMR spectra indicate exchange processes for both sulfido complexes. Their redox properties are discussed and contrasted with those observed for the parent fac-trioxo molybdenum(VI) complex. The primary synthetic route to mixed oxosulfido [MoO 3−nS nL] 2− complexes described here can be extended to other aminodicarboxylic ligands like iminodiacetic acid.

Addition and cycloaddition reactions of the nucleophilic oxo and sulfido complexes [tmtaa]Ti:X (X = O, S; tmtaa = dianion of 7,16-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAddition and cycloaddition reactions of the nucleophilic oxo and sulfido complexes [tmtaa]Ti:X (X = O, S; tmtaa = dianion of 7,16-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine)Chris E. Housmekerides, David L. Ramage, Christine M. Kretz, John T. Shontz, Robert S. Pilato, Gregory L. Geoffroy, Arnold L. Rheingold, and Brian S. HaggertyCite this: Inorg. Chem. 1992, 31, 22, 4453–4468Publication Date (Print):October 1, 1992Publication History Published online1 May 2002Published inissue 1 October 1992https://doi.org/10.1021/ic00048a006RIGHTS & PERMISSIONSArticle Views495Altmetric-Citations95LEARN 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