Hydrosulfido Complexes Research Articles

Hydrogen atom abstraction by a high-spin [FeIII=S] complex

Iron sulfur clusters are critical to a plethora of biological processes; however, little is known about the elementary unit of these clusters, namely the [Fe=S]n+ fragment. Here, we report the synthesis and characterization of a terminal iron sulfido complex. Despite its high spin (S = 5/2) ground state, structural, spectroscopic, and computational characterization provide evidence for iron sulfur multiple bond character. Intriguingly, the complex reacts with additional sulfur to afford an S = 3/2 iron(III) disulfido (S2 2-) complex. Preliminary studies reveal that the sulfido complex reacts with dihydroanthracene to afford an iron(II) hydrosulfido complex, akin to the reactivity of iron oxo complexes. By contrast, there is no reaction with the disulfido complex. These results provide important insight into the nature of the iron sulfide unit.

Synthesis of a Series of a Few Hydrosulfide Complexes of Cu(I). A μ3-SH-Bridged Rare Cubane-like Tetramer Showing Efficient Catalytic Activity toward Azide-Alkyne Cycloaddition.

A cubane-like tetranuclear hydrosulfido complex of Cu(I), [Cu4(SH)4(PPh3)4] (1), has been synthesized by the reaction of Cu(NO3)2·3H2O, NaSCOPh, and Cu(PPh3)2NO3 and characterized structurally. Complex 1 represents the first example of crystallographically characterized μ3-SH-bridged cubanoid hydrosulfide. By direct reactions of [(PPh3)2Cu(NO3)] and NaSH, neutral hydrosulfide complexes [Cu(SH)(PPh3)2]·C6H6 (2), [Cu2(SH)2(PPh3)3] (3), and [Cu2(SH)2(PPh3)4] (4) have also been synthesized and structurally characterized. Complex 2 is monomeric with a terminal hydrosulfide ligand. The other two, 3 and 4, are μ2-SH-bridged unsymmetrical and symmetrical dinuclear complexes, respectively. In the symmetric one (4), both Cu(I) ions are tetrahedrally coordinated while in the unsymmetric one (3), one Cu(I) ion is tetrahedral and the other one has a trigonal-planar coordination geometry. The catalytic activity of a hydrosulfido complex in a "click" azide-alkyne cycloaddition reaction has been explored for the first time, and complex 1 is found to be an efficient catalyst for the regioselective synthesis of glycoconjugate triazoles.

Sugar-Incorporated Chelating Bis-N-Heterocyclic Carbene Palladium Complexes. Synthesis, Structures, and Catalytic Ability for Suzuki-Miyaura Cross-Coupling Reactions in Water

Abstract Sugar-incorporated chelating bis-N-heterocyclic carbene ligand precursors 1,1′-bis(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)-3,3′-ethylene-diimidazolyl ([(bisNHC-C2)H2]2+) and 1,1′-bis(2,3,4,6-tetra-O-acetyl-β-d-glucopyranosyl)-3,3′-propylene-diimidazolyl ([(bisNHC-C3)H2]2+) were synthesized and used to prepare palladium complexes [Pd(bisNHC-C2)Cl2] and [Pd(bisNHC-C3)Cl2], respectively, by direct metallation reaction using dichlorobis(acetonitrile)palladium as a metal source. Catalytic abilities of the complexes for Suzuki-Miyaura coupling in aqueous media were examined and moderate TON (85,000) and TOF (170,000 h−1) were obtained. Because the terminal chloro ligands in the complexes were substituted with solvent molecules or chloride anion and hence 1H NMR spectra of the chloro complexes were complicated, hydrosulfido complexes [Pd(bisNHC-Cn)(SH)2] (n = 2 and 3) were prepared to confirm structures in solution. Dynamic behavior of flapping-wing motion of the bisNHC ligand in [Pd(bisNHC-C3)(SH)2] in solution was evaluated using the signals of the SH protons, which are inequivalent in 1H NMR spectra attributed to the chirality of the glucopyranosyl units.

Uranium(iv) terminal hydrosulfido and sulfido complexes: insights into the nature of the uranium-sulfur bond.

Herein, we report the synthesis and characterization of a series of terminal uranium(iv) hydrosulfido and sulfido complexes, supported by the hexadentate, tacn-based ligand framework (Ad,MeArO)3tacn3- (= trianion of 1,4,7-tris(3-(1-adamantyl)-5-methyl-2-hydroxybenzyl)-1,4,7-triazacyclononane). The hydrosulfido complex [((Ad,MeArO)3tacn)U-SH] (2) is obtained from the reaction of H2S with the uranium(iii) starting material [((Ad,MeArO)3tacn)U] (1) in THF. Subsequent deprotonation with potassium bis(trimethylsilyl)amide yields the mononuclear uranium(iv) sulfido species in good yields. With the aid of dibenzo-18-crown-6 and 2.2.2-cryptand, it was possible to isolate a terminal sulfido species, capped by the potassium counter ion, and a "free" terminal sulfido species with a well separated cation/anion pair. Spectroscopic and computational analyses provided insights into the nature of the uranium-sulfur bond in these complexes.

The Synthesis and Structures of Tris(2-pyridylseleno)methyl Zinc Compounds with κ2-, κ3-, and κ4-Coordination Modes

Tris(2-pyridylseleno)methane, [Tpsem]H, has been employed to synthesize the bis(trimethylsilyl)amido zinc complex [κ3-Tpsem]ZnN(SiMe3)2. The latter compound provides access to a variety of other [Tpsem]ZnX derivatives, which include the isocyanate complex [κ4-Tpsem]ZnNCO, the hydrosulfido complex [κ3-Tpsem]ZnSH, the sulfido complex {[κ3-Tpsem]Zn}2(μ-S), the 2 : 1 complex [κ2-Tpsem]2Zn and the pyridyl-2-selenolate complex [κ4-Tpsem]Zn-(κ2-SeC6H4N), thereby demonstrating that the [Tpsem] ligand can exhibit κ2-, κ3-, and κ4-coordination modes. Variable-temperature 1H NMR spectroscopic studies demonstrate that [κ3-Tpsem]ZnN(SiMe3)2, [κ3-Tpsem]ZnSH, and {[κ3-Tpsem]Zn}2(μ-S) are fluxional on the NMR timescale.

O-Alkylthiooxalato and dithiocarboxylato complexes of molybdenum and tungsten

The hydrosulfido complexes CpM(CO)3SH (M=Mo, W) react with one equivalent of O-alkyl oxalyl chlorides, RO2CCOCl, to form the corresponding O-alkylthiooxalato complexes CpM(CO)3SCOCO2R [M=Mo (1), W (2); R=Me (a), Et (b)]. The reaction of the hydrosulfido complexes with half equivalent of oxalyl or succinyl chlorides produces the bimetallic complexes [CpM(CO)3SCO]2 [M=Mo (3c), W (4c)] and [CpM(CO)3SCOCH2]2 [M=Mo (3d), W (4d)]. These new complexes have been characterized by elemental analysis, IR and 1H NMR spectroscopy. The solid state structures of CpMo(CO)3SCOCO2CH3 (1a) and CpW(CO)3SCOCO2CH2CH3 (2b) were determined by X-ray crystal structure analysis.

Sulfur containing platinum(ii) complexes with N-heterocyclic carbene ligands obtained by reactions of a hydrosulfido complex

A hydrosulfido platinum(ii) complex with a chelated N-heterocyclic carbene (NHC) ligand was oxidised with O(2) in the presence of excess hydrogen sulfide, to give a linear tetrasulfido complex, and without hydrogen sulfide, to give a thiosulfato-bridged dinuclear complex. The hydrosulfido complex also reacted with an acetato complex containing the chelating NHC platinum unit to afford a trinuclear platinum complex with two triply bridging sulfido ligands showing an equilibrium in solution between two isomers based on the arrangement of the chelating NHC ligands.

Diastereoselective Protonation, Substitution and Addition Reactions at Pseudotetrahedral Rhenium Complexes

AbstractThe chiral N,P ligand P(Me)(Ph)[8‐(2‐methylquinolinyl)] (3) was synthesized and separated into its enantiomers via diastereomeric palladium complexes. The reactions of 3 and (RP)‐3 with [CpRe(CO)(NO)(NCMe)]BF4 (7) gave thediastereomeric complexes [CpRe(CO)(NO){P(Me)(Ph)(C10H8N)}]BF4 [8 and (RRe,SP/SRe,SP)‐8], which, upon borohydride reduction, yielded the corresponding methyl complexes [CpRe(NO){P(Me)(Ph)(C10H8N)}(CH3)] [9 and (RRe,SP/SRe,SP)‐9]. Treatment of 9 with HBF4 under carefully controlled conditions gave the diastereomerically pure chelates [CpRe(NO){P(Me)(Ph)(C10H8N)}]BF4 [(RRe,SP/SRe,RP)‐10, (RRe,RP/SRe,SP)‐10 and (RRe,SP)‐10]. The chelate ring was opened with NaSH to produce the hydrosulfido complexes [CpRe(NO){P(Me)(Ph)(C10H8N)}(SH)] [(RRe,SP/SRe,RP)‐11, (RRe,RP/SRe,SP)‐11 and (RRe,SP)‐11]. Each step in this sequence proceeded with retention of configuration at rhenium. Complex 11 underwent acid‐promoted condensation with aldehydes to give thioaldehyde complexes [CpRe(NO){P(Me)(Ph)(C10H8N)}(S=CHR)]BF4 (12a–d, R = Ph, Me, 4‐C6H4OMe, C6F5). The addition of nucleophiles X– to 12a gave rhenium‐coordinated α‐chiral thiolate complexes [CpRe(NO){P(Me)(Ph)(C10H8N)}{SC(H)(Ph)(X)}] (13a–e, X = acac, PhCH2S, EtS, tBuS, CN) with 42–89 % de. The thiolate can readily be cleaved from the rhenium complex by a methylation/chelate ring‐closure strategy. The stereochemistry of the entire reaction sequence was corroborated for each step by X‐ray crystallography.

Reactivity of a rhenium hydroxo–carbonyl complex toward carbon disulfide: insights from theory

The reaction mechanism on the formation of the hydrosulfido complex [Re(SH)(CO)(3)(bipy)] via the reaction of [Re(OH)(CO)(3)(bipy)] with carbon disulfide was theoretically investigated at the B3LYP/6-31+G(d,p) (LANL2DZ+f for Re) level of theory taking into account bulk solvent effects by using the PCM-UAHF continuum model. The energetics of the process was also analyzed by means of single-point energy calculations by replacing the B3LYP functional by the B3PW91, M05, TPSS and TPSSh ones. The most favored mechanistic routes obtained by us uncover all the molecular rearrangements involved in the reactive process, thus allowing the enriching of the experimental mechanistic proposal. Besides, our findings permit to explain the assignment of the solution color change to the formation of [Re(SH)(CO)(3)(bipy)] when mixed CS(2) with [Re(OH)(CO)(3)(bipy)]. Finally, based on our mechanistic study is also possible to rationalize the formation of [Re(SC(S)OCH(3))(CO)(3)(bipy)] when [Re(OCH(3))(CO)(3)(bipy)] reacts with CS(2) and of TpZn-OCH(3) when methanol is present in the reaction of TpZn-OH with CS(2).

Synthesis and Reactivities of Sulfido-bridged Ir–W and Ir–Re Heterodinuclear Complexes with Imido Ligands

Abstract The iridium hydrosulfido complexes [Cp*IrH(SH)(PPh3)] (Cp* = η5-C5Me5) and [Cp*Ir(SH)2(PMe3)] were found to serve as effective building blocks for the synthesis of mono- and bis(sulfido)-bridged heterodinuclear complexes with a high-valent tungsten or rhenium–imido center.

Molybdenum S-bonded mono-thiocarboxylate complexes CpMo(CO) 3SCOR: Structure of CpMo(CO) 3SCOPh

Monothiocarboxylate complexes of molybdenum of the type CpMo(CO) 3SCOR [R = Me ( 1), CH 2Cl ( 2), Ph ( 3), 4-C 6H 4NO 2 ( 4), 3,5-C 6H 3(NO 2) 2 ( 5)] have been obtained by the reaction of the hydrosulfido complex, CpMo(CO) 3SH, with acid chlorides. Complexes 1– 5 have been characterized by IR and 1H-NMR spectroscopy, elemental analyses and by the single crystal X-ray diffraction of 3.

Monomeric and dimeric ruthenium thiooxalate complexes: Structures of CpRu(PPh 3) 2SCOCO 2Me and CpRu(dppe)SCOCO 2Et

The hydrosulfido complexes CpRu(L)(L′)SH react with one equivalent of O-alkyl oxalyl chlorides (ROCOCOCl) to form the corresponding O-alkylthiooxalate complexes CpRu(L)(L′)SCOCO 2R (L = L′ = PPh 3 ( 1), 1 2 dppe ( 2); L = PPh 3, L′ = CO ( 3); R = Me ( a), Et ( b)). The reactions of the hydrosulfido complexes with half equivalent of oxalyl chloride produce the bimetallic complexes [CpRu(L)(L′)SCO] 2 (L = L′ = PPh 3 ( 4), 1 2 dppe ( 5); L = PPh 3, L′ = CO ( 6)). The crystal structures of CpRu(PPh 3) 2SCOCO 2Me ( 1a) and CpRu(dppe)SCOCO 2Et ( 2b) are reported.

Syntheses of a series of trinuclear MIr 2 or pentanuclear MIr 4 bimetallic bis(selenido) and selenido–sulfido clusters (M=Pd, Pt, Fe, Co) from diiridium μ-bis(hydroselenido) and μ-hydroselenido–hydrosulfido complexes [{(η 5-C 5Me 5)IrCl} 2(μ-SeH)(μ-EH)] (E=Se, S)

Reactions of a diiridium μ-bis(hydroselenido) complex [Cp*IrCl(μ-SeH) 2IrCp*Cl] ( 1a; Cp*=η 5-C 5Me 5) with [MCl 2(cod)] (M=Pd, Pt; cod=1,5-cyclooctadiene), FeCl 2, and CoCl 2 readily afforded the bimetallic selenido clusters containing a trinuclear or a pentanuclear cores [(Cp*Ir) 2(MCl 2)(μ 3-Se) 2] (M=Pd, Pt ( 5), Fe ( 6)) and [(Cp*Ir) 4Co(μ 3-Se) 4][CoCl 3(MeCN)] 2 ( 8). Cluster 6 was converted to the latter-type bow-tie cluster [(Cp*Ir) 4Fe(μ 3-Se) 4][BPh 4] 2 ( 7) by treatment with an additional amount of 1a and excess NaBPh 4. Novel μ-hydroselenido–hydrosulfido complex [Cp*IrCl(μ-SeH)(μ-SH)IrCp*Cl] ( 3) was obtained by the reaction of [Cp*IrCl(μ-Cl) 2IrCp*Cl] with one equiv of H 2Se generated in situ from a NaSeH/HCl aq. mixture, followed by that with H 2S gas. Treatment of 3 with a range of transition metal compounds has shown that 3 can serve as a good precursor to synthesize a series of mixed-chalcogenido clusters in a rational manner; selenido–sulfido clusters derived from 3 include [(Cp*Ir) 2(MCl 2)(μ 3-Se)(μ 3-S)] (M=Pd, Pt, Fe ( 14)), [(Cp*Ir) 2{PtCl(PPh 3)}(μ 3-Se)(μ 3-S)]Cl ( 13), [(Cp*Ir) 4Co(μ 3-Se) 2(μ 3-S) 2][CoCl 3(MeCN)] 2 ( 15), and [(Cp*Ir) 4Fe(μ 3-Se) 2(μ 3-S) 2][BPh 4] 2. To determine the detailed structures, X-ray analyses have been undertaken for 5·1/2ClCH 2CH 2Cl, 6, 7, 8, 13·CH 2Cl 2, 14, and 15·CH 2Cl 2.

A new reactivity pattern of low-valent transition-metal hydroxo complexes: straightforward synthesis of hydrosulfido complexes via reaction with carbon disulfide.

A new basic transformation linking two important classes of transition metal compounds; namely, hydroxo and hydrosulfido complexes has been discovered.

Nucleophilic addition and substitution reactions on the sulfur atoms bound to two Ir atoms. Conversion of a hydrosulfido complex [(η5-C5Me5)2Ir2(μ-SH)3]Cl into a series of diiridium complexes with bridging thiolato ligands

Download options Please wait... Supplementary files Crystal structure data TXT (213K) Article information DOI https://doi.org/10.1039/B200689H Article type Paper Submitted 18 Jan 2002 Accepted 05 Jul 2002 First published 21 Aug 2002 Download Citation J. Chem. Soc., Dalton Trans., 2002, 3603-3610 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Nucleophilic addition and substitution reactions on the sulfur atoms bound to two Ir atoms. Conversion of a hydrosulfido complex [(η5-C5Me5)2Ir2(μ-SH)3]Cl into a series of diiridium complexes with bridging thiolato ligands F. Takagi, H. Seino, M. Hidai and Y. Mizobe, J. Chem. Soc., Dalton Trans., 2002, 3603 DOI: 10.1039/B200689H To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Search articles by author Fusao Takagi Hidetake Seino Masanobu Hidai Yasushi Mizobe

Syntheses, structures and properties of hydrosulfido-bridged diiridium and dirhodium complexes, [formula omitted

The reaction of [ Cp ∗ MCl (μ 2- Cl) 2 MCp ∗ Cl] ( M  Ir, Rh; Cp ∗ = η 5- C 5 Me 5) with excess H 2S gas for 5 min afforded the dobly bridged hydrosulfido complexes [ Cp ∗ MCl(μ 2- SH) 2 MCp ∗ Cl] ( 3: M = Ir, 4: M = Rh) which were further transformed into the triply bridged cationic hydrosulfido complexes [ Cp ∗ M(μ 2- SH) 3 MCp ∗] Cl ( 5·Cl: M = Ir, 6·Cl: M = Rh) by continuous stirring under H 2S. The molecular structures of 3, 4, 5 · [BPh 4] and 6·Cl·C 6H 6 were determined by X-ray analyses. The SH ligands in complexes 3 and 4 take anti configuration in the solid state, whilst these complexes exist as mixtures of the syn and anti isomers in solution. Strong hydrogen bonds between the Cl anion and two of the SH ligands were found in 5·Cl and 6·Cl, and were maintained in CDCl 4 solution. When complexes 3 and 4 were treated with NEt 3 at room temperature, the cubane-type sulfido clusters [ Cp ∗ M) 4(μ 4- S) 4] (M = Ir, Rh) were produced in high yields. In the reaction of 3, an intermediary complex, most probably [ Cp ∗ Ir(μ 2- S) 2 IrCp ∗] , was detected by 1H NMR.