Carbonyl complexes of manganese(I) with chelating phosphino-alkyl or -acyl ligands. Crystal and molecular structure of [Ph2PCH2CH2(O)CMn(CO)2(dppm)l

The phosphine Ph₂PCH₂CH₂Cl reacts with fac-[XMn(CO)₃(dppm)] (X = Cl or Br) in refluxing toluene to give the complexes cis,cis-[XMn(CO)₂(dppm)(Ph₂PCH₂CH₂Cl)] (I). Treatment of those species with Na amalgam in THF leads to the alkyl complex [Ph₂$\text{PCH}{}_2\text{CH}{}_2\text{M}$n(CO)₂(dppm)] (II), which does not react with CO under normal conditions but can be converted into cis,cis-[ClMn(CO)₂(dppm)(PPh₂Et)] by reacting with HCl (g) in ether. If the reduction of I with Na/Hg is carried out in the presence of CO the compound cis-[Ph₂$\text{PCH}{}_2\text{CH}{}_2\text{(O)CM}$n(CO)₂(dppm)] (III) is obtained. The latter has also been prepared directly from fac-[BrMn(CO)3(dppm)], Ph₂PCH₂CH₂Cl, and Na/Hg in THF, and characterized by X-ray crystallography. The crystals are monoclinic, space group P2₁/n; refinement gave R = 0.053 for 2593 reflections with I ? 2.5σ(I). The reaction of the complex fac-[O₃ClOMn(CO)₃(dppm)] with Ph₂PCH₂CH₂Cl in Cl₂CH₂ gives the salt fac-[Mn(CO)₃(dppm)(Ph₂PCH₂CH₂Cl)]ClO₄ which isomerizes to mer-[Mn(CO)₃(dppm)(Ph₂PCH₂CH₂Cl)]ClO₄ in boiling butanol. Both cationic carbonyl complexes give the acyl species III upon reduction with Na amalgam.     

Neutral and cationic dicarbonyl complexes of manganese (I) with diphosphines

The reaction of BrMn(CO)₅ with dppm in refluxing toluene gives the neutral compunds cis-cis-BrMn(CO)₂(dppm)₂ which has been shown by ³¹P NMR spectroscopy to have one dppm monodentate and the other bidendate. This complex reacts with TIPF₆ in dichloromethane solution to give the salt cis-[Mn(CO)₂-(dppm)₂]PF₆ or, if the reaction is carried out in the presence of CO, the salt mer-[Mn(CO)₃(dppm)₂]PF₆ which also has one monodentate dppm (by ³¹P NMR). The cationic complex cis-[Mn(CO)₂(dppm)₂]⁺ isomerizes to the transisomer when irradiated with UV light, while heating of the latter gives back the cis-isomer. The perchlorate salts of the cation cis-[Mn(CO)₂(dppm)₂⁺ can be prepared by reacting fac-O₃ClOMn(CO)₃(dppm) withdppm in refluxing toluene, and trans-[Mn(CO)₂(diphos)(diphos)′]⁺, diphos or diphos′ being dppm or dppe, by treating the fac-O₃ClMn(CO)₃(diphos) with dppm or dppe under UV irradiation.     

Cationic di- and mono-carbonyl complexes of manganese(I)

The complexes fac-O₃ClOMn(CO)₃(NN) (NN = 1,10-phenantroline (phen) or 2,2'bipyridine (bipy)) react with an excess of the ligands L [L = P(OR)₃ or P(OR)₂Ph, R = Me or Et] in refluxing ethanol to give cis-trans-[Mn(CO)₂-(NN)L₂]ClO₄, or the more highly substituted [Mn(CO)(NN)L₃]ClO₄ if the reaction is carried out under UV irradiation. Carbonylation at normal pressure of the latter complexes results in the formation of cis-cis-[Mn(CO)₂(NN)L₂]ClO₄, which undergo isomerization to the cis-trans isomer when heated in acetone.Treatment of fac-O₃ClOMn(CO)₃(dpe) (dpe = 1,2-bis(diphenylphosphino)-ethane] with bipy or phen in refluxing ethanol gives the corresponding cis-[Mn(CO)₂(NN)(dpe)]ClO₄ complexes, and irradiation of these with UV in the presence of an excess of P(OR)₃ (R = Ph, Et or Me) gives the monocarbonyls [Mn(CO)(NN)(dpe)L]ClO₄.     

Stereospecific syntheses of new manganese(I) isocyanide derivatives

Three series of cationic manganese(I) carbonyls are reported: [Mn(CO)_5-n(CNMe)_n(CNPh)]PF₆ (n = 1 → 4), [Mn(CO)_5-n(CNMe)(CNPh)_n]PF₆ (n = 1 → 4), and [Mn(dpe)(CO)_4-n(CNMe)_n]PF₆ (n = 1 → 4). Most of these compounds were prepared from a substituted metal carbonyl halide by replacement of halide ion by an added ligand (CNR or CO), such reactions requiring an added halide ion acceptor (Ag⁺ or AlCl₃). The added ligand enters the site of departing halide ion. It was possible to prepare isomers of many compounds reported, taking advantage of this stereospecificity. Structures of the products were defined, often unequivocally, by infrared and nmr spectroscopic data. Cyclic voltammetry showed that these compounds undergo one electron oxidations, the ease of oxidation determined by the nature of the ligand groups and the stereochemistry.     

Synthesis and Characterization of Polypiridine‐Based Rhenium(I) Complexes with Pyrazino[2,3‐f][1,10]phenanthroline

A series of tricarbonyl rhenium(I) complexes of the type fac‐[Re^I(CO)₃(ppl)(L)]^0/+, where ppl is pyrazino[2,3‐f][1,10]phenanthroline, and where L is Cl^?, TfO^?, 4‐(tert‐butyl)pyridine (^tBu‐py), 4‐methoxypyridine (MeO‐py), 4,4′‐bipyridyl (bpy), or 10‐(picolin‐4‐yl)phenothiazine (pptz), were synthesized and fully characterized. In all complexes, an increment in the electron‐acceptor properties of ppl compared to the free ligand was observed. This effect was more significant for pyridine‐type ligands, especially for pptz, compared to Cl^? or TfO^?. The properties of fac‐[Re(CO)₃(ppl)(pptz)]PF₆ were compared with those of the analogous compound fac‐[Re(CO)₃(dppz)(pptz)]PF₆, where dppz is dipyrido(3,2‐a : 2′,3′‐c)phenazine, the goal being to generate long‐lived excited charge‐transfer (CT) states. In this respect, fac‐[Re(CO)₃(ppl)(pptz)]PF₆ seems to be a promising candidate.     

Synthesis and characterization of rhenium(I) complexes with the polypyridinic quinone functionalized electron acceptor ligand [3,2-a:2′,3′-c]-benzo[3,4]-phenazine-11,16-quinone, Nqphen

In this work, the synthesis and characterization of fac-[Re(CO)₃(Nqphen)(L)]PF₆ complexes is reported. Nqphen is the quinone substituted acceptor ligand [3,2-a:2′,3′-c]-benzo[3,4]-phenazine-11,16-quinone, and L represents the donor monodentate pyridine substituted ligands 4-tert-butylpyridine (t-Bupy), 4-methoxypyridine (MeO-py) or 10-(4-picolyl)phenothiazine (py-PTZ). The complexes were synthesized by refluxing in methanol the metal precursor fac-Re(CO)₃(Nqphen)TfO (TfO = trifluoromethanesulphonate anion) with the corresponding L ligand. The UV-Vis spectra of the complexes are dominated by intense intraligand (IL) bands, and less intense metal ligand charge transfer (MLCT) bands with maxima in the 380-400 nm region. The IR shows the typical pattern for tricarbonyl Re complexes with facial (fac) geometry. An additional v(CO) stretching band, attributed to the quinone fragment of Nqphen, is observed.Electrochemical data indicate that the acceptor capacity of Nqphen is increased in the complexes with regard to the free ligand. This effect is sensitive to the nature of the L ligand, following the order: MeO-py < t-Bupy < py-PTZ, indicating therefore that the donor capacity of L affects the rest of the molecule. The results obtained for the fac-[Re (CO)₃(Nqphen)(pyPTZ)]PF₆ complex here reported were compared with those observed for the homologous complex fac-[Re(CO)₃(Aqphen)(L)]^0/+, with Aqphen = 12,17-dihydronaphtho[2,3-h]dipyrido[3,2-a:2′,3′-c]-phenazine-12,17-dione, and L = Cl⁻, TfO⁻, py-PTZ.     

Chelates formed by a constrained bis(diphenylphosphino)xylene; the crystal structures of [FeCl2(anphos)] and [RhCl(CO)(anphos-monoxide)]

The indan derived diphosphine, cis-1,3-(diphenylphosphino)indan (anphos) is synthesised by the addition of Ph₂P(BH₃)Li to cis-1,3-dibromoindan followed by deprotection with diethylamine. Anphos readily forms the bicyclic chelates [RhCl(CO)(anphos)], [PtCl₂(anphos)], [PtCl(Me)(anphos)] and [FeCl₂(anphos)]. The crystal structures of [FeCl₂(anphos)] and the monoxide complex, [RhCl(CO)(anphosO)] have been determined. Reaction of the diphosphine with [Rh(acac)(CO)₂] under moderate hydroformylation conditions catalysed the formation of 1-heptanal and branched aldehydes from 1-hexene in a ratio of 1.5:1.     

Reactions of diphosphineplatinum(II) oxalate complexes with phenylacetylene. Formation of phenylalkynylplatinum complexes

[Pt(C₂O₄)(dppe)] reacts thermally with PhCCH to produce [Pt(CCPh)₂(dppe)], which has been prepared by alternative routes. Similar treatment of [Pt(C₂O₄)(dppm)] initially produces [Pt(CCPh)₂(dppm)], which rearranges to give cis,cis-[Pt₂(CCPh)₄(μ-dppm)₂]. Reaction of [PtCl₂(dppm)] with PhCCH/KOH/18-crown-6, or with (PhCC)SnMe₃, gives [Pt(CCPh)₂(dppm)], which may be converted to the cis,cis-dimer by addition of oxalic acid. Ultraviolet irradiation or refluxing with a trace amount of dppm converts [Pt(CCPh)₂(dppm)] to trans,trans-[Pt₂(CCPh)₄(μ-dppm)₂], but the cis,cis-dimer is stable under these conditions. [Pt(C₂O₄)L₂] (L = PPh₃, PEt₃) complexes also react thermally with PhCCH to yield [Pt(CCPh)₂L₂] species.     

Synthesis of cationic carbonyl complexes of manganese(I) with bidentate ligands

Summary Bidentate ligands can readily replace acetone in thefac-[Mn(CO)₃(chel)(OCMe₂)]⁺ complexes or the perchlorate group fromfac-[Mn(CO)₃(chel)(OClO₃)] yieldingfac-[Mn(CO)₃(chel)(L-L)]⁺ or [{fac-Mn(CO)₃(chel)}₂(L-L)]²⁺ [chel = 1,10-phenanthroline (phen), 2,2-bipyridine (bipy), 1,2-bis(diphenylphosphine)ethane (dpe); L-L = bis(diphenylphosphine)methane (dpm), dpe, 1,4-bis(diphenylphosphine)butane (dpb), succinonitrile (suc), and glutaronitrile (glu)]. Some of these mononuclear complexes are precursors for binuclear complexes which are linked by bridging phosphines or nitriles.     

[M(CO)2(NO)], a new core in bioorganometallic chemistry: model complexes of [Re(CO)2(NO)] and [Tc(CO)2(NO)]

In this study selected bidentate (L²) and tridentate (L³) ligands were coordinated to the Re(I) or Tc(I) core [M(CO)₂(NO)]²⁺ resulting in complexes of the general formula fac-[MX(L²)(CO)₂(NO)] and fac-[M(L³)(CO)₂(NO)] (M = Re or Tc; X = Br or Cl). The complexes were obtained directly from the reaction of [M(CO)₂(NO)]²⁺ with the ligand or indirectly by first reacting the ligand with [M(CO)₃]⁺ and subsequent nitrosylation with [NO][BF₄] or [NO][HSO₄]. Most of the reactions were performed with cold rhenium on a macroscopic level before the conditions were adapted to the n.c.a. level with technetium (^99mTc). Chloride, bromide and nitrate were used as monodentate ligands, picolinic acid (PIC) as a bidentate ligand and histidine (HIS), iminodiacetic acid (IDA) and nitrilotriacetic acid (NTA) as tridentate ligands. We synthesised and describe the dinuclear complex [ReCl(μ-Cl)(CO)₂(NO)]₂ and the mononuclear complexes [NEt₄][ReCl₃(CO)₂(NO)], [NEt₄][ReBr₃(CO)₂(NO)], [ReBr(PIC)(CO)₂(NO)], [NMe₄][Re(NO₃)₃(CO)₂(NO)], [Re(HIS)(CO)₂(NO)][BF₄], [⁹⁹Tc(HIS)(CO)₂(NO)][BF₄], [^99mTc(IDA)(CO)₂ (NO)] and [^99mTc(NTA)(CO)₂(NO)]. The chemical and physical characteristics of the Re and Tc-dicarbonyl-nitrosyl complexes differ significantly from those of the corresponding tricarbonyl compounds.     

Permetalloplumbanes: Preparation of [Pb{Co(CO)3(L)}4] and [Pb{Fe(CO)2(NO)(L)}4].: Complexes containing four transition metal to lead bonds (L = tertiary arsine,phosphine or phosphite).

The sole and unexpected products from the reactions of a variety of lead (II) and lead (IV) compounds with [Co₂(CO)₆(L)₂] complexes (L = tertiary arsine, phosphine, or phosphite) in refluxing benzene solution are the blue, air-stable percobaltoplumbanes [Pb{Co(CO)₃(L)}₄]. These have also been obtained from the reaction of Na[Co(CO)₃(L)] (L  PBu₃ⁿ) with lead (II) acetate which with Na[Fe(CO)₂(NO)(L)] forms the isoelectronic [Pb{Fe(CO)₂(NO)(L)}₄] [L  P(OPh)₃]. The IR spectra of the complexes in the v(CO) and v(NO) regions are consistent with tetrahedral PbCo₄ or PbFe₄ fragments, trigonal bipyramidal coordination about the cobalt or iron atoms and linear PbCoAs, PbCoP, or PbFeP systems. Unlike [Pb{Co(CO)₄}₄], our complexes do not dissociate to [Co(CO)₃(L)]^? or [Fe(CO)₂(NO)(L)]^? ions when dissolved in donor solvents.     

Übergangsmetall—methylen-komplexe : XXXIV. Aufbau alicyclischer methylen-brucken nach einem modifizierten diazoalkan-verfahren

The mixed dinitrogen-isocyanide complexes mer-[ReCl(N₂)(CNMe)-{P(OMe)₃}₃] (I) and [ReCl(N₂)(CNMe)(PPh₃) {P(OEt)₃}₂] (II) are obtained by a novel route through reactions of CNMe with the organodiazenido species [ReCl₂(NNCOPh) {P(OMe)₃ }₃] and [ReCl₂(NNCOPh)(PPh₃){P(OEt)₃ }₂] (III, newly synthesized), whereas mer-[ReCl(N₂)(PPh₃) {P(OMe)₃ }₃] (IV) (which gives I by reaction with CNMe) is formed in the reaction of [$\text{ReCl}{}_2\text{(NNC}$OPh)(PPh₃)₂] with P(OMe)₃; the structure of complex I is authenticated by X-ray analysis.     

A new route to mer-Tricarbonyls of manganese(I) containing N-donor chelate ligands

It has been shown that new mer-tricarbonyls mer-[Mn(CO)₃L(tmed)]ClO₄, (tmed = N,N,N′,N′-tetramethylethylenediamine, L = P(OMe)₃, P(OEt)₃, P(O-iPr)₃) can be readily obtained from the reaction between fac-Mn(CO)₃(tmed)Br, AgClO₄, and L at room temperature, whereas at 0°C fac-isomers are produced. The opposite is the case for L = CN-t-Bu; mer-[Mn(CO)₃(CN-t-Bu)(tmed)]ClO₄ is observed at 0°C, and the fac-isomer is stable at 25°C.     

8-Oxyquinolate iridium(I) complexes and their oxidative-addition reactions

The novel sixteen-electron complex [Ir(Oq)(COD)] (Oq = 8-oxyquinolate; COD = 1,5-cyclooctadiene) adds monodentate phosphines, phosphites or activated olefins irreversibly to give pentacoordinate iridium(I) complexes of the type [Ir(Oq)(COD)L] (L = PPh₃, P(OPh)₃, maleic anhydride or tetracyano-ethylene). Reaction of [Ir(Oq)(COD)] with some diphosphines leads to substitution products of the general formula [Ir(Oq)(diphos)] (diphos = 1,2-bis(diphenylphosphino)ethane or cis-1,2-bis(diphenylphosphino)ethylene). Carbon monoxide displaces the COD group from the complexes giving either [Ir(Oq)(CO)₂] or [Ir(Oq)(CO)L], and the latter undergo oxidative addition reactions with SnCl₄, Me₃SiCl, Me₃SnCl, MeI, allylbromide, PhCOCl, MeCOCl, Cl₂, Br₂, TlCl₃ and HCl leading to novel iridium(III) complexes.     

Substituted derivatives of [Fe2(CO)9] and [Ru2(CO)9] and their susceptibility to electrophilic attack: X-ray crystal structure of [Fe2(μ-Br)(CO)4{μ-(C6H5O)2PN(C2H5)P(OC6H5)2}2]PF6

Bis- and, in particular, tetra-substituted ditertiary phosphine and diphosphazane derivatives of [Fe₂(CO)₉] and [Ru₂(CO)₉], readily synthesised by reaction of the appropriate bidentate ligand with [Fe₂(CO)₉] and [Ru₃(CO)₁₂], respectively, are very susceptible to electrophilic attack by reagents such as halogens and protons; the solid state structure of one of the products [Fe₂(μ-Br)(CO)₄ {μ-(PhO)₂PN(Et)P(OPh)₂}₂]PF₆ has been determined by X-ray crystallography.     

Regiospecificity in the reaction of [Fe2(η-C5H5)2(CO)4-n(CNMe)n] (n  02) with mercury(II) halides

The reactions of [Fe₂(η-C₅H₅)₂(CO)₂(L)(CNMe)] (L  CO or CNME) with HgX₂ (X  Cl, Br or I) give [Fe(η-C₅H₅)(CO)₂HgX] and [Fe(η-C₅H₅)(L)-(CNMe)X] as the sole products in ca. quantitative yields; this is consistent with the previously proposed mechanism for the reactions of electrophiles with polynuclear metal carbonyl derivatives.     

Synthesis and spectroscopy of cis-configured mononuclear palladium(II) and platinum(II) complexes of chalcogeno o-carboranes and structures of [Pt(SCboPh)2(dppm)], [Pt(SeCboPh)2(dppm)], [Pt(SCboS)(PMe2Ph)2] and [Pt(SCboS)(PMePh2)2]

The reactions of [MCl₂(P^∩P)] and [MCl₂(PR₃)₂)] with 1-mercapto-2-phenyl-o-carborane/NaSeCb^oPh and 1,2-dimercapto-o-carborane yield mononuclear complexes of composition, [M(SCb^oPh)₂(P^∩P)], [M(SeCb^oPh)₂(P^∩P)] (M = Pd or Pt; P^∩P = dppm (bis(diphenylphosphino)methane), dppe (1,2-bis(diphenylphosphino)ethane) or dppp (1,3-bis(diphenylphosphino)propane)) and [M(SCb^oS)(PR₃)₂] (2PR₃ = dppm, dppe, 2PEt₃, 2PMe₂Ph, 2PMePh₂ or 2PPh₃). These complexes have been characterized by elemental analysis and NMR (¹H, ³¹P, ⁷⁷Se and ¹⁹⁵Pt) spectroscopy. The ¹J(Pt–P) values and ¹⁹⁵Pt NMR chemical shifts are influenced by the nature of phosphine as well as thiolate ligand. Molecular structures of [Pt(SCb^oPh)₂(dppm)], [Pt(SeCb^oPh)₂(dppm)], [Pt(SCb^oS)(PMe₂Ph)₂] and [Pt(SCb^oS)(PMePh₂)₂] have been established by single crystal X-ray structural analyses. The platinum atom in all these complexes acquires a distorted square planar configuration defined by two cis-bound phosphine ligands and two chalcogenolate groups. The carborane rings are mutually anti in [Pt(SCb^oPh)₂(dppm)] and [Pt(SeCb^oPh)₂(dppm)].     

Synthesis and spectroscopy of cis-configured mononuclear palladium(II) and platinum(II) complexes of chalcogeno o-carboranes and structures of [Pt(SCboPh)2(dppm)], [Pt(SeCboPh)2(dppm)], [Pt(SCboS)(PMe2Ph)2] and [Pt(SCboS)(PMePh2)2]

The reactions of [MCl₂(P^∩P)] and [MCl₂(PR₃)₂)] with 1-mercapto-2-phenyl-o-carborane/NaSeCb^oPh and 1,2-dimercapto-o-carborane yield mononuclear complexes of composition, [M(SCb^oPh)₂(P^∩P)], [M(SeCb^oPh)₂(P^∩P)] (M = Pd or Pt; P^∩P = dppm (bis(diphenylphosphino)methane), dppe (1,2-bis(diphenylphosphino)ethane) or dppp (1,3-bis(diphenylphosphino)propane)) and [M(SCb^oS)(PR₃)₂] (2PR₃ = dppm, dppe, 2PEt₃, 2PMe₂Ph, 2PMePh₂ or 2PPh₃). These complexes have been characterized by elemental analysis and NMR (¹H, ³¹P, ⁷⁷Se and ¹⁹⁵Pt) spectroscopy. The ¹J(Pt–P) values and ¹⁹⁵Pt NMR chemical shifts are influenced by the nature of phosphine as well as thiolate ligand. Molecular structures of [Pt(SCb^oPh)₂(dppm)], [Pt(SeCb^oPh)₂(dppm)], [Pt(SCb^oS)(PMe₂Ph)₂] and [Pt(SCb^oS)(PMePh₂)₂] have been established by single crystal X-ray structural analyses. The platinum atom in all these complexes acquires a distorted square planar configuration defined by two cis-bound phosphine ligands and two chalcogenolate groups. The carborane rings are mutually anti in [Pt(SCb^oPh)₂(dppm)] and [Pt(SeCb^oPh)₂(dppm)].     

[Fe2(μsb‐CO)(CO)3(NO)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]: Synthese,Kristallstruktur und Koordinationsisomerie

[Fe₂(μ_sb‐CO)(CO)₃(NO)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)]: Synthesis, X‐ray Crystal Structure and Isomerization Na[Fe₂(μ‐CO)(CO)₆(μ‐P^tBu₂)] ( 1 ) reacts with [NO][BF₄] at —60 °C in THF to the nitrosyl complex [Fe₂(CO)₆(NO)(μ‐P^tBu₂)] ( 2 ). The subsequent reaction of 2 with phosphanes (L) under mild conditions affords the complexes [Fe₂(CO)₅(NO)L(μ‐P^tBu₂)], L = PPh₃, ( 3a ); η‐dppm (dppm = Ph₂PCH₂PPh₂), ( 3b ). In this case the phosphane substitutes one carbonyl ligand at the iron tetracarbonyl fragment in 2 , which was confirmed by the X‐ray crystal structure analysis of 3a . In solution 3b loses one CO ligand very easily to give dppm as bridging ligand on the Fe‐Fe bond. The thus formed compound [Fe₂(CO)₄(NO)(μ‐P^tBu₂)(μ‐dppm)] ( 4 ) occurs in solution in different solvents and over a wide temperature range as a mixture of the two isomers [Fe₂(μ_sb‐CO)(CO)₃(NO)(μ‐P^tBu₂)(μ‐dppm)] ( 4a ) and [Fe₂(CO)₄(μ‐NO)(μ‐P^tBu₂)(μ‐dppm)] ( 4b ). 4a was unambiguously characterized by single‐crystal X‐ray structure analysis while 4b was confirmed both by NMR investigations in solution as well as by means of DFT calculations. Furthermore, the spontaneous reaction of [Fe₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 5 ) with NO at —60 °C in toluene yields a complicated mixture of products containing [Fe₂(μ‐CO)(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 6 ) as main product beside the isomers 4a and 4b occuring in very low yields.     

Reactions of trans-[RuCl2(CO)2(PEt3)2] with 1,1-dithiolates: Stepwise formation of cis-[Ru(CO)(PEt3)(S2X)] (X = CNMe2, CNEt2, COEt,P(OEt)2, PPh2)

Trans-[RuCl₂(CO)₂(PEt₃)₂] reacts with two equivalents of a series of 1,1-dithiolate ligands to form the bis(dithiolate) complexes, cis-[Ru(CO)(PEt₃)(S₂X)₂] (X = CNMe₂, CNEt₂, COEt, P(OEt)₂, PPh₂). Two intermediates have been isolated; trans-[Ru(PEt₃)₂Cl(CO){S₂P(OEt)₂}] and trans-[Ru(PEt₃)₂(CO)(η¹-S₂COEt)(η²-S₂COEt)], allowing a simple reaction scheme to be postulated involving three steps; (i) initial replacement of cis carbonyl and chloride ligands, (ii) substitution of the second chloride, (iii) loss of a phosphine. Thermolysis of cis-[Ru(CO)(PEt₃)(S₂CNMe₂)₂] with Ru₃(CO)₁₂ in xylene affords trinuclear [Ru₃(μ₃-S)₂(PEt₃)(CO)₈] as a result of dithiocarbamate degradation. Crystal structures of cis-[Ru(CO)(PEt₃)(S₂X)₂] (X = NMe₂, COEt), trans-[Ru(PEt₃)₂Cl(CO){S₂P(OEt)₂}], trans-[Ru(PEt₃)₂(CO)(η¹-S₂COEt)(η²-S₂COEt)] and [Ru₃(μ₃-S)₂(PEt₃)(CO)₈] are reported.