Cationic dihydridoiridium(III) complexes of nitriles

The reaction of [IrL(CO)(PPh₃)₂]ClO₄ (PPh₃ = triphenylphosphine) with H₂ produces new cationic dihydridoiridium(III) complexes of nitriles (L), [Ir(H)₂L(CO)(PPh₃)₂]ClO₄ [L = CH₃CN (1), CH₃CH₂CN (2), CH₃CH₂CH₂CN (3) and C₆H₅CN (4)], where nitriles are coordinated through the nitrogen atom. Proton NMR spectral data for complexes 1–4 suggest that the two hydrides in each complex are cis to each other and trans to CO and nitrogen (nitrile), and the two PPh₃ are trans to each other.     

Zur Kenntnis der Chemie der Metallcarbonyle und der Cyano-Komplexe in flüssigem ammoniak : XL. Über die Reaktion kationischer Cyclopentadienyl-carbonyl-nitrosyl-Komplexe des Mangans und Rheniums mit flüssigem Ammoniak

The reactions of the cationic complexes [CpMn(CO)₂NO]⁺, [MeCpMn(CO)₂NO]⁺ (Cp = η⁵-C₅H₅, MeCp = η⁵-C₅H₄CH₃), [CpRe(CO)₂NO]⁺, [CpMn(CO)(L)NO]⁺ (L = PPh₃, PEt₂Ph, AsPh₃, CNMe, CNEt), {[CpMn(CO)NO]₂Me₂PC₂H₄PMe₂}²⁺ and {CpMn(CO)NO]₂Ph₂PC₂H₄PPh₂}²⁺ with liquid NH₃ yield the neutral carbamoyl complexes CpMn(CO)(NO)CONH₂, MeCpMn(CO)(NO)CONH₂, CpRe(CO)(NO)CONH₂, CpMn(L)(NO)CONH₂ (L = PPh₃, PEt₂Ph, AsPh₃, CNMe, CNEt), [CpMn(NO)CONH₂]₂Me₂PC₂H₄PMe₂ and [CpMn(NO)CONH₂]₂Ph₂PC₂H₄PPh₂. Properties and reactions of these new compounds are described.     

Electrochemical behaviour of [Ru(L)(CO)2Cl2] [Ru(L)(CO)Cl3][Me4N] and [Ru(L)(CO)2(CH3CN)2][CF3SO3]2 complexes (L = 2,2′- bipyridine or 4,4′-isopropoxycarbonyl-2,2′-bipyridine)

The clectrochemical behaviour of the complexes [Ru^II(L)(CO)₂Cl₂], [Ru^II(L)(CO)Cl₃][Me₄N] and [Ru^II(L)(CO)₂(CH₃CN)₂][CF₃SO₃]₂ (L = 2,2′-bipyridine or 4,4′-isopropoxycarbonyl-2,2′-bipyridine) has been investigated in CH₃CN. The oxidation of [Ru(L)(CO)₂Cl₂] produces new complexes [Ru^III(L)(CO)(CH₃CN)₂Cl]²⁺ as a consequence of the instability of the electrogenerated transient Ru^III species [Ru^III(L)(CO)₂Cl₂]⁺. In contrast, the oxidation of [Ru^II(L)(CO)Cl₃][Me₄N] produces the stable [Ru^III(L)(CO)Cl₃] complex. In contrast [Ru^II(L)(CO)₂(CH₃CN)₂][CF₃SO₃]₂ is not oxidized in the range up to the most positive potentials achievable. The reduction of [Ru^II(L)(CO)₂Cl₂] and [Ru^II(L)(CO)₂(CH₃CN)₂][CF₃SO₃]₂ results in the formation of identical dark blue strongly adherent electroactive films. These films exhibit the characteristics of a metal-metal bond dimer structure. No films are obtained on reduction of [Ru^II(L)(CO)Cl₃][Me₄N]. The effect of the substitution of the bipyridine ligand by electron-withdrawing carboxy ester groups on the electrochemical behaviour of all these complexes has also been investigated.     

Potential inhibitors of DNA topoisomerase II: ruthenium(II) poly-pyridyl and pyridyl-azine complexes

In search of new DNA probes a series of new mono and binuclear cationic complexes [RuH(CO)(PPh₃)₂(L)]⁺ and [RuH(CO)(PPh₃)₂(-μ-L)RuH(CO)(PPh₃)₂]²⁺ [L=pyridine-2-carbaldehyde azine (paa), p-phenylene-bis(picoline)aldimine (pbp) and p-biphenylene-bis(picoline)aldimine (bbp)] have been synthesized. The reaction products were characterized by microanalyses, spectral (IR, UV-Vis, NMR and ESMS and FAB-MS) and electrochemical studies. Structure of the representative mononuclear complex [RuH(CO)(PPh₃)₂(paa)]BF₄ was crystallographically determined. The crystal packing in the complex [RuH(CO)(PPh₃)₂(paa)]BF₄ is stabilized by intermolecular π-π stacking resulting into a spiral network. Topoisomerase II inhibitory activity of the complexes and a few other related complexes [RuH(CO)(PPh₃)₂(L)]⁺ {L=2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) and 2,3-bis(2-pyridyl)-pyrazine (bppz)} have been examined against filarial parasite Setaria cervi. Absorption titration experiments provided good support for DNA interaction and binding constants have also been calculated which were found in the range 1.2 × 10³-4.01 × 10⁴ M⁻¹.     

Transformation of neutral rhenium compounds during electrospray ionization mass spectrometry

Four neutral rhenium compounds were examined by electrospray ionization mass spectrometry. Acetonitrile solutions of (Ind)Re(CO)₃ (Ind = indenyl) and (Cp)Re(CO)₃ (Cp = cyclopentadienyl) gave rise to [Re(CO)₃(CH₃CN)₃]⁺ ions. This is indicative of a reaction with the solvent, although these compounds do not react with acetonitrile under regular laboratory conditions. In contrast, (Ind)Re(CO)₂(butyne) and (Cp)Re(CO)₂(butyne) did not lose their aromatic hydrocarbon ligand upon ionization; the predominant product ions generated upon electrospray ionization were [(Ind)Re(CO)(CH₃CN)(butyne)]⁺ and [(Cp)Re(CO)(CH₃CN)(butyne)]⁺, respectively.     

单氢钌配合物与水和2,2,2-三氟乙醇的作用机理

利用原位¹H和³¹P NMR对单氢钌配合物TpRu(PPh₃)(CH₃CN)H [Tp＝hydrotris(pyrazolyl)borate]与H₂O和酸性HOCH₂CF₃的反应进行了研究, 结果显示相应的反应产物分别是TpRu(PPh₃)(CH₃CN)(OH) 和TpRu(PPh₃)(CH₃CN)(OCH₂CF₃). 观察到反应过程中Ru-H…HOH和Ru-H…HOCH₂CF₃分子间的氢键作用. 提出了生成TpRu(PPh₃)(CH₃CN)(OH)和TpRu(PPh₃)(CH₃CN)(OCH₂CF₃)的不同作用机理. 在水存在下, TpRu(PPh₃)(CH₃CN)H 与H₂O反应, 经过中间体TpRu(PPh₃)(H₂O)H和TpRu(PPh₃)(OH)(η²-H₂)生成产物TpRu(PPh₃)(CH₃CN)(OH). 而TpRu(PPh₃)(CH₃CN)H与酸性HOCH₂CF₃反应时, 单氢配体被质子化形成中间体[TpRu(PPh₃)(CH₃CN)- (η²-H₂)](OCH₂CF₃), 进而转变成产物TpRu(PPh₃)(CH₃CN)(OCH₂CF₃). TpRu(PPh₃)(CH₃CN)(OCH₂CF₃)与H₂作用, 经中间体TpRu(PPh₃)(HOCH₂CF₃)H生成TpRu(PPh₃)(η²-H₂)H.     

Preparation of new (η5-C5H4CH3)Mn(NO)(PPh3) and (η7-C7H7)Mo(CO)-(PPh3) complexes

The complex (η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)I has been prepared by the reaction of NaI with [(η⁵-C₅H₄CH₃)Mn(NO)(CO)(PPh₃)]⁺ and also by the reaction of [(η⁵-C₅H₄CH₃)Mn(NO)(CO)₂]⁺ with NaI followed by PPh₃. This iodide compound reacts with NaCN to yield (η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)CN which is ethylated by [(C₂H₅)₃O]BF₄ to yield [(η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)(CNC₂H₅)]⁺. Both [(η⁵-C₅H₄CH₃)Mn(NO)(CO)₂]⁺ and [(η⁵-C₅H₄CH₃)Mn(NO)(PPh₃)(CO)]⁺ react with NaCN to yield [(η⁵-C₅H₄CH₃)Mn(NO)(CN)₂]^?. This anion reacts with Ph₃SnCl to yield cis-(η⁵-C₅H₄CH₃)Mn(NO)(CN)₂SnPh₃ and with [(C₂-H₅)₃O]BF₄ to yield [(η⁵-C₅H₄CH₃)Mn(NO)(CNC₂H₅)₂]⁺. The reaction of (η⁵-C₅-H₄CH₃)Mn(NO)(PPh₃)I with AgBF₄ in acetonitrile yields [(η⁵-C₅H₄CH₃)Mn-(NO)(PPh₃)(NCCH₃)]⁺. The complex (η⁵-C₅H₄CH₃)Mn(NO)(CO)I, produced in the reaction of [(η⁵-C₅H₄CH₃)Mn(NO)(CO)₂]⁺ with NaI, is not stable and decomposes to the dimeric complex (η⁵-C₅H₄CH₃)₂Mn₂(NO)₃I for which a reasonable structure is proposed. Similar dimers can be prepared from the other halide salts. The reaction of (η⁷-C₇H₇)Mo(CO)(PPh₃)I with NaCN yields (η⁷-C₇-H₇)Mo(CO)(PPh₃)CN which is ethylated by [(C₂H₅)₃O]BF₄ to yield [(η⁷-C₇H₇)-Mo(CO)(PPh₃)(CNC₂H₅)]⁺. The interaction of this molybdenum halide complex with AgBF₄ in acetonitrile and pyridine yields [(η⁷-C₇H₇)Mo(CO)(PPh₃)-(NCCH₃)]⁺ and [(η⁷-C₇H₇)Mo(CO)(PPh₃)(NC₅H₅)]⁺, respectively. Both (η⁵-C₅-H₄CH₃)Mn(NO)(PPh₃)I and (η⁷-C₇H₇)Mo(CO)(PPh₃)I are oxidized by NOPF₆ to the respective 17-electron cations in acetonitrile at ?78°C but revert to the neutral halide complex at room temperature. This result is supported by electrochemical data.     

Protonation of Cp(CO)(PPh3) RuCCPh: Formation of cationnic phenylacetylene and phenylvinylidene complexes and subsequent reaction with ethylene oxide to form the net [2 + 3] cycloadduct [Cp(CO)(PPH3)Ru=CCH(Ph)CH2CH2O]+

Protonation of the alkynyl complex Cp(CO)(PPh₃)RuCCPh (1) at low temperature affords quantitatively the vinylidened complex [Cp(CO)(PPh₃)RuCCH(Ph)]⁺ (3), which upon warming to room temperature forms an equilibrium with the η²-phenylacetylene complex [Cp(CO)(PPh₃)Ru(η²-HCCPh)]⁺ (4), with the latter predominating. Subsequent reaction with ethylene oxide yields the cyclic oxacarbene complex [Cp(CO)(PPH₃)Ru=CCH(Ph)CH₂CH₂O]⁺ (5), which can be regarded as the result of a net [3+2] cycloaddition reaction between 3 and ethylene oxide. Depronation of 5 affords teh corresponding neutral cyclic vinyl complex [Cp(CO)(PPH₃)RuC=C(Ph)CH₂CH₂O]⁺ (6), which can in turn be protonated to regenerate 5 in a diastereoselective manner. The structures of complexes 5 and 6 were determined by X-ray crystallography.     

Stereospecific synthesis and redox properties of ruthenium(II) carbonyl complexes bearing a redox-active 1,8-naphthyridine unit

Two stereoisomers of cis-[Ru(bpy)(pynp)(CO)Cl]PF₆ (bpy = 2,2′-bipyridine, pynp = 2-(2-pyridyl)-1,8-naphthyridine) were selectively prepared. The pyridyl rings of the pynp ligand in [Ru(bpy)(pynp)(CO)Cl]⁺ are situated trans and cis, respectively, to the CO ligand. The corresponding CH₃CN complex ([Ru(bpy)(pynp)(CO)(CH₃CN)]²⁺) was also prepared by replacement reactions of the chlorido ligand in CH₃CN. Using these complexes, ligand-centered redox behavior was studied by electrochemical and spectroelectrochemical techniques. The molecular structures of pynp-containing complexes (two stereoisomers of [Ru(bpy)(pynp)(CO)Cl]PF₆ and [Ru(pynp)₂(CO)Cl]PF₆) were determined by X-ray structure analyses.     

The use of ferrocene in organometallic synthesis: A two-step preparation of cyclopentadienyliron acetonitrile and phosphine cations via photolysis of cyclopentadienyliron tricarbonyl or arene cations

UV photolysis of [CpFe^II(CO)₃]⁺ PF6₆^? (I) or [CpFe^II(η⁶-toluene)]⁺ PF₆^?? (II) in CH₃CN in the presence of 1 mole of a ligand L gives the new air sensitive, red complexes [CpFe^II(NCCH₃)₂L]⁺PF₆^? (III, L = PPh₃; IV; L = CO; VIII, L = cyclohexene; IX, L = dimethylthiophene) and the known air stable complex [CpFe^II(PMe₃)₂(NCMe)]⁺ PF₆^? (V). The last product is also obtained by photolysis in the presence of 2 or 3 moles of PMe₃. In the presence of dppe, the known complex [CpFe^II (dppe)(NCCH₃)]⁺ (XI) is obtained. Complex III reacts with CO under mild conditions to give the known complex [CpFe(NCCH₃)(PPh₃)CO]⁺ PF₆^? (X). UV photolysis of I in CH₃CN in the presence of 1-phenyl-3,4-dimethylphosphole (P) gives [CpFe^IIP₃]⁺ PF₆^? (XII); UV photolysis of II in CH₂Cl₂ in the presence of 3 moles of PMe₃ or I mole of tripod (CH₃C(CH₂Ph₂)₃) provides an easy synthesis of the known complexes [CpFe^II(PMe₃)₃]⁺ PF₆^? (VII) or [CpFe^IIη³-tripod]⁺ PF₆^t- (XIII). Since I and II are easily accessible from ferrocene, these photolytic syntheses provide access to a wide range of piano-stool cyclopentadienyliron(II) cations in a 2-step process from ferrocene.     

Reactivity of 6-(2-tolyl)- and 6-(2,6-xylyl)-2,2′-bipyridines with palladium(II) derivatives. Selective C(sp)H vs. C(sp)H activation

Two new 6-substituted 2,2′-bipyridines, L, 6-(2-tolyl)bipy, L¹, and 6-(2,6-xylyl)bipy, L², have been synthesized. Their reactions with Na₂[PdCl₄] or {Pd(OAc)₂} afford either 1:1 adducts [Pd(L)X₂] (X=Cl, OAc) or five-membered cyclometallated derivatives [Pd(L¹-H)X] arising from C(sp²)H activation. From the chloro-alkyl intermediates [Pd(L)(Me)Cl], in the presence of Na[BAr′₄] (Ar′=3,5-(CF₃)₂C₆H₃), cationic species [Pd(L)(Me)(S)]⁺ (L=L¹, L²; S=CH₃CN) can be obtained. At variance, in less coordinating solvents, e.g. dichloromethane, unexpected activation of a C(sp³)H bond occurs with loss of methane, to afford 6-membered cyclometallated derivatives. The latter species were isolated as [Pd(L-H)(PPh₃)][BAr′₄].     

Donor ligand, basal ligand and solvent effects on the equilibrium constants of triphenylphosphinecobalt(III) Schiff base complexes with phosphite ligands

The equilibrium constants and the thermodynamic parameters were spectrophotometrically measured for the 1:1 adduct formation of [Co(Salen)(PPh₃)]ClO₄.H₂O, and [Co(7,7′-Me₂Salen)(PPh₃)]ClO₄.H₂O as acceptors, with P(OR)₃ (R = methyl, ethyl, and i-propyl) as donors, in acetonitrile (CH₃CN) and dimethylformamide (DMF) as solvents at constant ionic strength (I = 0.1 M NaClO₄), and various temperatures (t = 10–50 °C). Our results revealed the following trends: stability of the cobalt(III) Schiff base complexes toward a given phosphite donor, [Co(7,7′-Me₂Salen)(PPh₃)]⁺ < [Co(Salen)(PPh₃)]⁺; binding of the donors (phosphites) toward a given cobalt(III) Schiff base complex, P(OEt)₃ > P(OMe)₃ > P(O-ⁱPr)₃; influence of solvent on the stability of a given cobalt(III) Schiff base complex toward a given phosphite donor, CH₃CN < DMF.     

Reactions of cationic rhodium(I) carbonyl compounds with nucleophiles to form alkoxo,carboalkoxy and carboxylato complexes. Part II

Summary The rhodium(I) carbonyl compounds [Rh(CO)L₂2] [BF₄]. 1/2CH₂Cl_nn2 (L = PPh₂ or AsPh₃) react with the nucleophiles OMe⁻, RCOO⁻ (R = Me, Et) under nitrogen to form [Rh(OR)(CO)L₂] (1)–(2) and [Rh(OOCR)(CO)L₂] (7)–(₁₀), respectively. Addition of [Rh(CO)₂(PPh₃)₂]-[BF ₄] to OMe⁻ under nitrogen produces [Rh(COOMe)-(CO) (PPh₃)₂]-MeOH (3), whilst reactions of [Rh(CO)-(PPh₃)₂] [BF₄]·1/2CH₂Cl₂ and [Rh(CO)₂(PPh₃)₂] [BF₄] with OR_- (R = Me, Et or n-Pr) in the presence of CO produce [Rh(COOR)(CO)₂(PPh₃)₂] (4)–(6). The products have been characterised by i.r., ¹H, ³¹P, ¹³Cn.m.r. spectroscopy and elemental analysis.     

The electrochemistry of organotransition-metal complexes : II. Formation and reactivity of the radical cations [trans-Fe(CO3(PR3)2]+ and [Fe(CO)3 (Ph2 PCH2 CH2 PPh2)]+

[Fe(CO)₃ L₂] (L = PPh₃, PPh₂Me, P(OPh)₃ or P(NMe₂)₃; L₂ = Ph₂ PCH₂ CH₂ PPh₂⁺) undergo reversible one-electron oxidations to give the radical cations [Fe(CO)₃L₂]⁺ which have been studied by IR and ESR spectroscopy.     

Erratum

The hydrido-thiocarbonyl osmium(II) complexes OsH₂(CS)(PPh₃)₃, OsHCl(CS)(PPh₃)₃, OsH(OClO₃)(CS)(PPh₃)₃, OsHCl(CS)(CNR)(PPh₃)₂ and [OsH(CS)(CO)(PPh₃)₃]⁺, (R = p-tolyl), have been derived from OsCl₂(CS)(PPh₃)₃ and [OsH(CS)(CO)(PPh₃)₃]⁺, the latter can be deprotonated to give the zerolavent complex, Os(CS)(CO)(PPh₃)₃.     

Synthesis of transition-metal Lewis acid adducts of trans-[ReCl(CNR)(Ph2PCH2CH2PPh2)2] (R = alkyl). A chemical and a quantum-chemical study of electrophilic β-addition to ligating isocyanide

Treatment of trans-[ReCl(CNR)(dppe)₂] (R = Me or Bu^t, dppe = Ph₂PCH₂CH₂ PPh₂) with CoCl₂(THF)_1.5, [ReOCl₃(PPh₃)₂] or [WCl₄L₂] (L = PPh₃ or PEtPh₂) affords the dinuclear adducts [ReCl(CN(M)R)(dppe)₂] (M = CoCl₂(THF), ReOCl₃(PPh₃) or WCl₄L, respectively) (formed via electrophilic β-addition of the electron-acceptor molecules to the isocyanide ligands), which undergo dissociation oxidation (for M = CoCl₂(THF) or ReOCl₃(PPh₃)). These reactions are considered in the light of results of extended Hückel calculations.     

Ruthenium(II) complexes containing bidentate Schiff bases and their antifungal activity

The reactions of ruthenium(II) complexes, [RuHCl(CO)(PPh₃)₂(B)] [B = PPh₃, pyridine (py) or piperidine (pip)], with bidentate Schiff base ligands derived by condensing salicylaldehyde with aniline, o-, m- or p-toluidine have been carried out. The products were characterised by analytical, i.r., electronic, ¹H-n.m.r. and ³¹P-n.m.r. spectral studies and are formulated as [RuCl(CO)(L)(PPh₃)(B)] (L = Schiff base anion; B = PPh₃, py or pip). An octahedral structure has been tentatively proposed for the new complexes. The Schiff bases and the new complexes were tested in vitro to evaluate their activity against the fungus Aspergillus flavus.     

Electron transfer versus nucleophilic pathways in the ion-pair annihilation of organoborate anions by carbonylmanganese(I) cations

Substituted carbonylmanganese cations [Mn(CO)₅L]⁺, where L=py, PPh₃ and PPh₂Me, readily react with various organoborate anions (tetramethylborate, methyltriphenylborate and tetraphenylborate) in THF solution to afford a mixture of dimanganese carbonyls, hydridomanganese carbonyls and alkylmanganese carbonyls. The formation of the dimanganese carbonyl dimers as well as the hydridomanganese carbonyls suggests the involvement of 19-electron carbonylmanganese radicals that stem from an initial electron transfer. On the other hand, the acetonitrile-substituted analogue [Mn(CO)₅(CH₃CN)]⁺ reacts with the same borate anions to afford the alkylated RMn(CO)₅, where R=CH₃ and C₆H₅, as the sole carbonylmanganese product. As such, this alkylative annihilation is best formulated as a direct attack on the carbonyl carbon by the borate nucleophile. The two different pathways can be understood in terms of the balance between the electrophilicity of the carbonyl ligand and the electron affinity of the carbonylmanganese cation.     

Synthesis,stability and reactivity of cationic carbonyl complexes of rhodium(I)

Summary Trans-[RhCl(CO)L₂] (L = PPh₃, AsPh₃ or PCy₃) react with AgBF₄ in CH₂Cl₂ to give the novel species [Rh-(CO)L₂]⁺ [BF₄]^–.nCH₂Cl₂ (n = 1/2 or 1 1/2) (1–3), which we believe to be stabilised by weak solvent interaction. The corresponding stibine compound cannot be isolated by the same process, instead [Rh(CO)₂(SbPh₃)₃]⁺ [BF₄]^– (7) is formed when the reaction is carried out in the presence of CO. When reactions designed to prepare [Rh(CO)L₂]⁺ [BF₄]^– are performed in the presence of CO, or [Rh(CO)L₂]⁺ [BF₄]^– complexes are reacted with CO, [Rh(CO)₂L₂]⁺ [BF₄]^– (L = PPh₃, AsPh₃ or PCy₃) (4–6) are formed. If Me₂CO is used as solvent in the preparation of [Rh(CO)L₂]⁺ [BF₄]^– (L = PPh₃ or AsPh₃), then the products are the four-coordinate [Rh(CO)L₂-(Me₂CO)]⁺ [BF₄]^– (8,9) species. The complexes have been characterised by i.r., ³¹P and ¹H n.m.r. spectroscopy and elemental analyses.     

Acetylene Dithiolate Linking up the [Tp′W(CO)(CN)] Moiety with RuII or PdII

A series of heterodinuclear complexes with acetylene dithiolate (acdt^2?) as the bridging moiety were synthesised by a facile one‐pot procedure that avoided use of the highly elusive acetylene dithiol. Generation of the W–Ru complex [Tp′W(CN)(CO)(C₂S₂)Ru(η⁵‐C₅H₅)(PPh₃)] (Tp’=hydrotris(3,5‐dimethylpyrazolyl)borate) and the W–Pd complexes [Tp′W(CN)(CO)(C₂S₂)Pd(dppe)] and [Tp′W(CO)₂(C₂S₂)Pd(dppe)][PF₆] (dppe=1,2‐bis(diphenylphoshino)ethane), which exhibit a [W(η²‐κ²‐C₂S₂)M] core (M=Ru, Pd), was accomplished by using a transition‐metal‐assisted solvolytical removal of the Me₃Si‐ethyl thiol protecting groups. All intermediate species of the reaction have been fully characterised. The highly coloured W–Ru complex [Tp′W(CN)(CO)(C₂S₂)Ru(η⁵‐C₅H₅)(PPh₃)] shows reversible redox chemistry, as does the prototype complex [Tp′W(CO)₂(C₂S₂)Ru(η⁵‐C₅H₅)(PPh₃)][PF₆]. Single crystal X‐ray diffraction and IR, EPR and UV/Vis spectroscopic studies in conjunction with DFT calculations prove the high electronic delocalisation of states over the acdt^2? linker. Comparative studies revealed a higher donor strength and more pronounced dithiolate character of acdt^2? in [Tp′W(CN)(CO)(C₂S₂)Ru(η⁵‐C₅H₅)(PPh₃)] relative to [Tp′W(CO)₂(C₂S₂)Ru(η⁵‐C₅H₅)(PPh₃)]⁺. In addition, the influence of the overall complex charge on the metric parameters was investigated by single‐crystal X‐ray diffraction studies with the W–Pd complexes [Tp′WL₂(C₂S₂)Pd(dppe)] (L=(CN^?)(CO) or (CO)₂). The central [W(C₂S₂)Pd] units exhibit high structural similarity, which indicates the extensive delocalisation of charge over both metals.