Überraschende Reaktionen an O-Methyl-1,1-dithiooxalaten

Surprising Reactions on O-Methyl-1,1-dithiooxalates The O-methyl-1,1-dithiooxalate ligand (i-dtoMe) reacts with metal^II-acetylacetonates of d⁸ metal centers (Ni^II, Pd^II) forming mononuclear mixed ligand complexes with two remarkable aspects: The formation of a perthioligand, first time described for thiooxalates, and the first example of a nucleophilic attack of a CH-acidic compound (acetylacetonate) on dithiocarbon of coordinated dithiocompounds (here i-dtoMe). X-ray structure is shown for Ph₄P[(ptoMe)Ni(i-dtoMeacac)].     

Neue Gemischtligandenkomplexe mit Perthiocarboxylaten

New Mixed Ligand Complexes with Perthio Carboxylates Solutions of O-methyl-1,1-dithiooxalate (i-dtoMe) and metal(II)-chlorides (Ni^II, Pd^II) in the molar ratio 2:1 react with equimolar amounts of homonuclear bischelates of other 1,1- and 1,2-dithio-compounds L (L = i-mnt, Etxan, dto) to mixed ligand complexes M(ptoMe)L with spontaneous convertion of the 1,1-dithiooxalate into the corresponding perthio ligand (ptoMe) by sulfur insertion. Tetraphenylphosphonium-(1,1-dicyanoethene-2,2-dithiolato)(O-methyl-1,1 -perthio-oxalato)niccolat(II), Ph₄P[Ni(i-mnt)(ptoMe)], crystallizes in the monoclinic space group P2₁/n with a = 11.019(2) Å, b = 13.648(3) Å, c = 20.882(3) Å, β = 92.565(7)°. The formation of the perthio ligand is confirmed by ¹³C-NMR.     

Oxydation von Nickel(0)-Komplexen mit cyclischen Carbonsäureamiden

Oxidation of Nickel(0) Complexes by Cyclic Imides of Dicarbonic Acids Normally, phthalimide (PI? H) or succinimide (SI? H) react with nickel(0) complexes — (dipy)Ni(COD) or (Ph₃P)₂Ni(C₂H₄) — by oxidative addition. The reaction of PI? H and the strong reductant (dipy)Ni(COD) is initiated by a one-electron transfer. Depending on the solvent, the resulting ion pair affords (dipy)Ni^I(PI) by spontaneous fragmentation or (dipy)Ni^II(H)(PI) by cage collaps. No interaction is found between the weak reductant (Ph₃P)Ni(C₂H₄) and PI? H. Phosphine-containing nickel(0) complexes are electrophilically attacked by the acid NH group of SI? H. Hydrido complexes of nickel(0), such as (Cy₃P)₂Ni(H)(SI), or secondary products of them, such as [(SI)Ni(THF)]₂NH, are formed. On the other hand, the reaction with (dipy)Ni(COD) affords only the binuclear substitution product [(dipy)Ni]₂(SI? H)(THF). In solution prolongated heating of (dipy)Ni(PI)(THF)_0,5 results in a partial decarbonylation. In contrast to the reaction of (dipy)Ni(COD) and cyclic carbonic acid anhydrides, no definite metalla rings but by an interaction with the solvent, benzamide is formed. With (dipy)Ni(COD) maleinimide does not react like on NH-acidic compound but like a polar olefine by substitution.     

Binukleare Nickel(II)‐Komplexe mit Oxalamidinaten als Brückenliganden: Synthese und Strukturen von Verbindungen mit planarer,tetraedrischer, tetragonal‐pyramidaler und oktaedrischer Koordination

Binuclear Nickel(II) Complexes with Oxalamidinates as Bridging Ligands: Synthesis and Struktures of Compounds with Planar, Tetrahedral, Tetragonal‐pyramidal, and Octahedral Coordination Oxalamidines R¹–NH–C(=NR²–C(=NR²)–NH–R¹ react selectively with Ni(acac)₂ under formation of the planar complexes [(acac)Ni(oxalamidinate)Ni(acac)]. Two crystal structures of the binuclear complexes with R = R′ = Ph ( 1 ) or p‐tolyl ( 2 ) show that the bridging oxalamidinates bind as bidendate ligands at each Nickel(II) atom. In contrast, the more sterically demanding fragment (Ph₃P)NiBr can only coordinate at sterically less demanding oxalamidinates to form complexes of the type [(Ph₃P)NiBr]₂(oxalamidinate) with tetrahedral coordination of Ni^II found by X‐ray analyses. Oxalamidines containing additional donor atoms in the side arms react very different, but in each case under formation of binuclear complexes, such as [(acac)₂Ni]₂( H₂E ) ( 8 ) (with R¹: –(CH₂)₃PPh₂, R²: p‐tolyl) in which the oxalamidine acts as bidentate neutral P,N‐ligand and the Ni^II atom has an octahedral environment. H₂F (with R¹: –(CH₂)₃PPh₂, R²: Mesityl), however, yields the planar complex [(acac)Ni]₂( F ) ( 9 ) with dianionic oxalamidinate under elimination of acetylacetone. There is no coordination of the donor groups of the side arms in the solid state of complex 9 , in contrast to the analogous binuclear complex [(acac)Ni]₂( H ) 10 (R¹: –CH₂–CH₂‐2‐pyridyl, R²: Mesityl). In this complex a distorted tetragonal‐pyramidal coordination of Ni^II is achieved. 2 reacts with an excess of LiCH₃ under elimination of the oxalamidinate to form the cluster compound Li₄(THF)₄Ni₂Me₈ in very good yields, while 9 yields the THF poorer cluster Li₂(THF)₂Li₂Ni₂Me₈ under similar conditions.     

Aryl Phosphine Nickel(II) and Palladium(II) Complexes with N,O‐Amino‐carboxylate Chelate Ligands [(Aryl)(R3P)M(N,O‐α‐aminocarboxylate)](M = Ni,Pd). Catalysts for the Polymerization of Olefins

The title complexes [(Aryl)(R₃P)M(N,O‐α‐aminocarboxylate)] (M = Ni, Pd) were synthesized by reaction of [(o‐tolyl)(Ph₃P)₂NiBr] or of [(p‐Me₃CC₆H₄)(o‐tolyl₃P)Pd(μ‐Br)]₂ with the anions of α‐amino acids. The spectroscopic data indicate that the nickel complexes are formed as mixtures of isomers, whereas for the palladium complexes only one isomer is observed. The complex [(o‐tolyl)(Ph₃P)Ni(glycinate)] is – in the presence of AlEt₃ – a highly active catalyst for the polymerization of ethylene [up to 1800 kg PE / (mol Ni·h)] and gives polymers with remarkably high molecular weights (up to 900.000 g/mol) and with few branchings.     

Schwefeldioxid als Ligand und Synthon. XIII. Reaktionen von Isocyanid-tris(triphenylphosphan)nickel(0)-Komplexen mit Schwefeldioxid und N-p-Tolylsulfinylamin

Sulfur Dioxide as Ligand and Synthon. XIII. Reactions of Isocyanide-tris(triphenylphosphane)nickel(0) Complexes with Sulfur Dioxide and N-p-tolylsulfinylamine Reactions of the isocyanide-tris(triphenylphosphane)-nickel(0) complexes [(RNC)Ni(PPh₃)₃] (R = ^tBu, Cy, PhCH₂, p-TosCH₂) with SO₂ and p-TolNSO are described. The sulfur dioxide and N-p-tolylsulfinylamine complexes obtained by PPh₃ ligand substitution have been characterized by means of i.r. and ³¹P n.m.r. spectra. The X-ray crystal structure of [(Ph₃P)₂(CyNC)Ni(SO₂)] · 0.5 PhMe and (Ph₃P)(^tBuNC)Ni(η²-p-TolNSO) have been determined.     

Reaction of hydride complexes of nickel with carbon monoxide

Conclusions When the hydride complexes of nickel (Ph₃P)₃Ni(H)Br and [(Ph₃P)₃Ni(H)(CH₃CN)]⁺BF₄ ^– are reacted with CO, the Ni-H bond is cleaved and carbonyl complexes of Ni(0) are formed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1919–1920, August, 1981.     

Binuclear organometallic compounds VIII. Oxidative addition of Si-H or Si-Cl compounds to low valent Fe, Co, or Ni complexes stabilised by mono- or bi-dentate phosphines

The reactions of [(Ph₃P)₄Ni], [(Ph₃P)₃CoN₂], [(dp)₂Ni], [(dp)₂CoH], [(dp)₂Fe(C₂H₄)] or [(dp)₂FeH₂] (dp = Ph₂PCH₂CH₂Ph₂P) with Ph_nSiCl_4-n (n = 1, 2, or 3), Ph_nSiH_4-n, X₃SiH (X = Cl or Et), or R₂ClSiH (R = Ph or Me) have been investigated. Solid complexes were isolated which, for the most part, were insoluble in non-polar solvents. Assignments of structures are therefore incomplete, and are based on microanalysis, IR spectra, analogies with established reactions, and (in some cases) chemical degradation. Evidence is presented for the following: (i) for Ni^II, products from [(Ph₃P)₄Ni] and HSiXX′X″ (XX′X″ = Ph₃, Ph₂H or PhH₂), the cyclic [(Ph₃P)₂NiSiCl₂]₂, and the five-coordinate [(dp)₂-NiX]⁺[SiCl₃]^- (X = H or Cl₃Si); (ii) for Co^III, the six-coordinate cis-octahedral [(dp)₂CoH₂]⁺ [SiXX′X″]^- (XX′X″ = Cl₃, Cl₂Me, ClMe₂, or ClPh₂); and for Fe^II, the four-coordinate [(dp)FeH(SiCl₃)] and the six-coordinate [(dp)₂Fe(X)SiCl₃] (X = H, Cl, or Cl₃Si).     

Monometallic Ni0 and Heterobimetallic Ni0/AuI Complexes of Tripodal Phosphine Ligands: Characterization in Solution and in the Solid State and Catalysis

The tridentate chelate nickel complexes [(CO)Ni{(PPh₂CH₂)₃CMe}] ( 2 ), [(CO)Ni{(PPh₂CH₂CH₂)₃SiMe}] ( 6 ), and [Ph₃PNi{(PPh₂CH₂CH₂)₃SiMe}] ( 7 ), as well as the bidentate complex [(CO)₂Ni{(PPh₂CH₂)₂CMeCH₂PPh₂}] ( 3 ) and the heterobimetallic complex [(CO)₂Ni{(PPh₂CH₂)₂CMeCH₂Ph₂PAuCl}] ( 4 ), have been synthesized and fully characterized in solution. All ¹H and ¹³C NMR signal assignments are based on 2D‐NMR methods. Single crystal X‐ray structures have been obtained for all complexes. Their ³¹P CP/MAS (cross polarization with magic angle spinning) NMR spectra have been recorded and the isotropic lines identified. The signals were assigned with the help of their chemical shift anisotropy (CSA) data. All complexes have been tested regarding their catalytic activity for the cyclotrimerization of phenylacetylene. Whereas complexes 2 – 4 display low catalytic activity, complex 7 leads to quantitative conversion of the substrate within four hours and is highly selective throughout the catalytic reaction.     

Spectral and electrochemical characterization of bimetallic complexes of a novel 32-membered unsymmetrical [N<Subscript>12</Subscript>] macrocycle

Reactions of a 32-membered [N₁₂] macrocyclic ligand, L.2HClO₄ with metal salts MCl₃ (M=Cr or Fe) and MCl₂ (M=Co, Ni or Cu) have produced complexes of stoichiometries M₂LCl₄(ClO₄)₂ and M₂LCl₂(ClO₄)₂, respectively. However, reactions with [M(Ph₃P)₂Cl₂] (M=Co or Ni) and [(η⁵-C₅H₅)Ni(Ph₃P)I] follow a ligand substitution path resulting in products with stoichiometries M₂LCl₂(ClO₄)₂ and [(η⁵-C₅H₅)₂Ni₂L(ClO₄)₂], respectively. The mode of bonding and geometry of the complexes have been derived on the basis of i.r., ligand field spectral and magnetic susceptibility measurements. EPR of Cu^II complex shows anisotropy with , G < 4.0 and orbital reduction factor . Thermodynamic first ionic association constants (K₁) and the corresponding free energy change (ΔG) of complexes in DMSO have been determined and discussed. Cyclic voltammetric studies indicate the presence of a quasi-reversible redox couples Cr^III/II, Co^II/I, Ni^II/I, Ni^II/III and Cu^II/I in solutions suggesting flexible nature of the macrocyclic cavity.     

Reactivity ofN-trimethylsilyl-imidazole and 2-methylimidazole; synthesis and physico-chemical studies on transition metal imidazolates and mixed ligand imidazolates

Summary N-trimethylsilylimidazole andN-trimethylsilyl-2-methylimidazole react with MCl₂ yield [ML₂] (M=Ni or Cu; L =imidazolate or 2-methylimidazolate). The complex [NiL₂] can also be prepared from [Ni(Ph₃P)₂Cl₂]; [Cu(Ph₃P)₃Cl] yields [Cu(Ph₃P)₂L]. The complexes are soluble in most non-polar organic solvents and experimentally determined molecular weights suggest they are monomers in solution. Magnetic susceptibility measurements and reflectance and electronic spectral studies at room temperature are commensurate with square-planar geometry for [CuL₂]. Although, the ligand field spectrum for [NiL₂] is compatible with a square-planar geometry, the anomalous _eff value suggests that the ground electronic state of Ni^II in [NiL₂] is near the magnetic cross-over point concomitant with the singlet-triplet spin state equilibrium. The i.r. spectra exhibit characteristic imidazolate and Ph₃P ring vibrations, andv(M–N) andv(M–P) stretching vibrations at the appropriate frequencies. The synthesis and characterization of a Cu^II complex, formulated as [Cu(Ph₃P)₂LCl], with tetrahedral structure is described.     

Arene C?H Amination at Nickel in Terphenyl–Diphosphine Complexes with Labile Metal–Arene Interactions

The meta‐terphenyl diphosphine, m‐P₂, 1 , was utilized to support Ni centers in the oxidation states 0, I, and II. A series of complexes bearing different substituents or ligands at Ni was prepared to investigate the dependence of metal–arene interactions on oxidation state and substitution at the metal center. Complex (m‐P₂)Ni ( 2 ) shows strong Ni⁰–arene interactions involving the central arene ring of the terphenyl ligand both in solution and the solid state. These interactions are significantly less pronounced in Ni⁰ complexes bearing L‐type ligands ( 2‐L : L=CH₃CN, CO, Ph₂CN₂), Ni^IX complexes ( 3‐X : X=Cl, BF₄, N₃, N₃B(C₆F₅)₃), and [(m‐P₂)Ni^IICl₂] ( 4 ). Complex 2 reacts with substrates, such as diphenyldiazoalkane, sulfur ylides (Ph₂S?CH₂), organoazides (RN₃: R=para‐C₆H₄OMe, para‐C₆H₄CF₃, 1‐adamantyl), and N₂O with the locus of observed reactivity dependent on the nature of the substrate. These reactions led to isolation of an η¹‐diphenyldiazoalkane adduct ( 2‐Ph₂CN₂ ), methylidene insertion into a Ni? P bond followed by rearrangement of a nickel‐bound phosphorus ylide ( 5 ) to a benzylphosphine ( 6) , Staudinger oxidation of the phosphine arms, and metal‐mediated nitrene insertion into an arene C? H bond of 1 , all derived from the same compound ( 2 ). Hydrogen‐atom abstraction from a Ni^I–amide ( 9 ) and the resulting nitrene transfer supports the viability of Ni–imide intermediates in the reaction of 1 with 1‐azido‐arenes.     

Diphosphine Compounds,Part III: UV/Visible Spectroscopy and Novel Routes to Functionalized Diphosphine-M(CO)6 Complexes (M = W,Mo, or Cr)

Reaction of coordinated (diphenylphosphino)methane and ketones or aldehydes have been characterized by ³¹P{H¹}-NMR, ¹H{³¹P}-NMR, and UV/vis spectroscopy in dichloromethane. Group VI metals hexacarbonyl [M(CO)₆ where M = Cr, Mo, and W] reacted with (diphenylphosphino)methane, [(Ph₂P)₂CH₂], to give [(OC)₄M{(Ph₂P)₂CH₂}] depending upon the reaction conditions. Condensation of [(CO)₄M{(Ph₂P)₂CH₂}] with different ketones or aldehydes forms [(CO)₄M{(Ph₂P)₂C = CR₁R₂}]. Complexes of the types [(OC)₄M{(Ph₂P)₂C = CR₁R₂}] reacted with hydrazine in a Michael addition to give [(CO)₄M{(Ph₂P)₂CHC(R₁R₂)NHNH₂}](1.3a–e), which condensed with different ketones and aldehydes to give complex of the type [(CO)₄M{(Ph₂P)₂CHC(R₁R₂)NHN = C(R₃)] (1.4a–e). The structures of the complexes are discussed on the basis of elemental analysis (EA), IR,¹H-NMR, ³¹P-NMR spectroscopic data, and FAB mass spectra. The UV/vis spectra show two absorption bands with the low energy band moving to lower energy with increasing substitution on the (diphenylphosphino) methane (dppm) (a bathochromic effect).     

A New Domain of Reactivity for High‐Valent Dinuclear [M(μ‐O)2M′] Complexes in Oxidation Reactions

The strikingly different reactivity of a series of homo‐ and heterodinuclear [(M^III)(μ‐O)₂(M^III)′]²⁺ (M=Ni; M′=Fe, Co, Ni and M=M′=Co) complexes with β‐diketiminate ligands in electrophilic and nucleophilic oxidation reactions is reported, and can be correlated to the spectroscopic features of the [(M^III)(μ‐O)₂(M^III)′]²⁺ core. In particular, the unprecedented nucleophilic reactivity of the symmetric [Ni^III(μ‐O)₂Ni^III]²⁺ complex and the decay of the asymmetric [Ni^III(μ‐O)₂Co^III]²⁺ core through aromatic hydroxylation reactions represent a new domain for high‐valent bis(μ‐oxido)dimetal reactivity.     

Synthese und Kristallstrukturen von [(Ph3As)2CCN–MnBr3], [(Ph3As)2CCN–CoBr3] und [(Ph3As)2CCN]+CuBr2–

Syntheses and Crystal Structures of [(Ph₃As)₂CCN–MnBr₃], [(Ph₃As)₂CCN–CoBr₃], and [(Ph₃As)₂CCN]⁺CuBr₂^– The di(arsa)acetonitrilium bromide [(Ph₃As)₂CCN]Br reacts with the anhydrous dibromides of manganese and cobalt in acetonitrile to form the molecular complexes [(Ph₃As)₂CCN–MBr₃] [M = ( 1 ), Co( 2 )] with zwitterionic structures. With copper(I)bromide, however, the ionic compound [(Ph₃As)₂CCN]⁺CuBr₂^– ( 3 ) is formed. All complexes are characterized by IR spectroscopy and by crystal structure analyses. 1 and 2 crystallize isotypically with each other in the space group P 1 with two formula units per unit cell. The MBr₃^– fragments in the molecular complexes are connected to the N atom of the [(Ph₃As)₂CCN]⁺ cation showing bond angles C–N–Mn of 156.9° and C–N–Co of 161°, and distances Mn–N of 215.6 pm and Co–N of 201 pm. In 3 , on the other hand, (space group C2/c, Z = 4) the ions [(Ph₃As)₂CCN]⁺ and the linear Br–Cu–Br^– ion are to be found concurrent but separate.     

The use of hydrogenated Schiff base ligands in the synthesis of multi-metallic compounds II

Tris(2-hydroxybenzylaminoethyl)amine (H₃L) complexes of nickel, copper and zinc are investigated as potential metallo-ligands ([(H_xL)M]; x = 0, 1: M = Ni, Cu, Zn). The homometallic complexes formed are dimetallic ([{(HL)Ni}Ni(OAc)₂] and [{(L)Zn}ZnCl]), tetrametallic ([{(L)Cu}Cu]₂²⁺) and hexametallic ([{(L)Ni}Ni₂(μ-OH)₂(OEt)(OH₂)]₂). Hetero-dimetallic complexes can be formed with [(HL)Ni] and copper chloride ([{(HL)Ni}CuCl₂]) or zinc bromide ([{(HL)Ni}ZnBr₂]). The metallo-ligand acts as a chelating agent using phenolate pairs. The remaining phenolate either does not coordinate or can be used to increase the number of metals included in the scaffold from two to four or six. Not all combinations are possible and [(HL)Cu]⁺ produces a charge separated species with zinc chloride rather than a complex. An exchange reaction is observed to take place when [(HL)Zn]⁺ is treated with the halides of nickel or copper producing [(HL)M]⁺ (M = Ni, Cu, respectively).     

Synthesis and Basic Coordination Properties of Side‐chain Functionalized Bis‐phosphonio‐benzophospholides

Salts containing bis‐phosphonio‐benzophospholide cations 2 a – d with an additional donor site in one of the phosphonio‐moieties were synthesized either via quaternisation of the Ph₂P moiety in the neutral phosphonio‐benzophospholide 3 , or via ring‐closure of the functionalized bis‐phosphonium ion 6 . The Ph₂P‐substituted cation 2 d formed chelate complexes [M(k²P,P′‐ 2 d )(CO)_n]⁺ with M(CO)_n = Ni(CO)₂, Fe(CO)₃, Cr(CO)₄. In the latter case, competition between formation of the chelate and a complex [Cr(kP‐ 2 d )₂(CO)₄]²⁺ was observed, and interpreted as a consequence of antagonism between the stabilizing chelate effect and destabilizing ligand–ligand repulsions. The formation of stable Pd^II and Pt^II complexes of 2 d suggests that the chelate effect may also overcome the kinetic inhibition which so far prevented isolation of complexes of these metals with bis‐phosphonio‐benzophospholides. The newly synthesized ligands and complexes were characterized by spectroscopic data, and an X‐ray crystal structure analysis of 2 a [Br]. The reactivity of chelate complexes towards Ph₃P indicates that the ring phosphorus atom is a weaker donor than the pendant Ph₂P‐group.     

Spectral and electro-chemical characterization of transition metal complexes of a modified [N<Subscript>6</Subscript>] macrocycle. A mimic to cyclic hexapeptide

The 16-membered modified [N₆] macrocylic ligand (L), a mimic to cyclic, hexapeptide is reacted with MCl₂ and MCl₃ resulting in complexes with stoichiometrices [MLCl₂] (M = Cr, Mn, Co, Ni, Cu), [MLCl₃] (M = Pt, Pd) and [MLCl₂]Cl (M = Fe, Ru). Its reactions with the precursors [M(Ph₃P)₂Cl₂] (M = Co, Ni, Pt, Pd) follow a ligand displacement path affording the final products which do not contain coordinated Ph₃P. Complexes have been characterized from results of elemental analyses, conductometric, magnetic susceptibility, i.r. and u.v.–vis (ligand field) spectral studies. Magnetic susceptibility and ligand field spectral data are consistent with a hexacoordinate geometry for Cr²⁺, Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺ and Cu²⁺ and four coordinate square-planar geometry for Pt²⁺ and Pd²⁺. Molecular orbital computations using CSChem ultra MOPAC software for an optimized minimum energy plot of the structure shows that the ligand binds metal ions as a tetradentate (N,N,N,N) chelating agent. Cyclic voltammetric studies indicate formation of stable reversible or quasi-reversible redox couples in solutions, which corroborates a kinetic stability of these complexes in their variable oxidation states.     

Magnetic properties of biacetyldihydrazone complexes

Summary Magnetic susceptibilities of the biacetyldihydrazone (BdH) complexes [M(BdH)₃](NO₃)₂ (M = Co^II, Ni^II, Cu^II or Zn^II), [Fe(BdH)₃](NO₃)₃, [M(BdH)₃](Ni(dto)₂] (M = Co^II, Ni^II or Zn^II; dto = dithiooxalate), [(BdH)₂Cu(dto)Ni(dto)] and [Fe(BdH)₃]₂[Ni(dto)₂]₃ have been studied in the 4.2–295 K range. Zn^II complexes are diamagnetic, and complexes of Ni^II, Cu^II and Fe^III obey the Curie-Weiss law. The Co^II complexes behave anomalously and the results are interpreted in terms of a high spinlow spin equilibrium.     

Metallorganische Lewis-Säuren. L. Addition von Pentacarbonylrhenium- und Triphenylphosphangold-Kationen an anionische Dithiolato-Metall-Komplexe als S-Nukleophile

Organometallic Lewis Acids. L. Addition of Pentacarbonylrhenium and Triphenylphosphinegold Cations to Anionic Dithiolato Metal Complexes as S-Nucleophiles The organometallic Lewis Acids Ph₃PAuNO₃ ( 1 ) and (CO)₅ReFBF₃ ( 2 ) react with the dithiolato metal complexes (Bu₄N)₂[M(mnt)₂] (mnt = m aleo n itrildi t hiolato, M = Ni, Cu, Pt, Zn) and (Bu₄N)₂[Zn(dmit)₂] (dmit = d i m ercapto i sotri t hiono) to give the complexes (Ph₃PAu)₂mnt ( 3 ), (Bu₄N)[Ph₃PAu(mnt)] ( 4 ), (Ph₃PAu)₂Pt(mnt)₂ ( 5 ), (Ph₃PAu)₂dmit ( 10 ) and [(CO)₅Re]₂Ni(mnt)₂ ( 6 ), (Bu₄N){[(CO)₅Re]M(mnt)₂} (M = Ni, Pt, 7, 8 ), [(CO)₅Re]₂(mnt)₂ ( 9 ) and [(CO)₅Re]₂Ni(dmit)₂ ( 11 ), respectively. The compounds 3, 4 and 5 have been characterized by x-ray structural analysis. In 4 the chelate ligand is symmetrically coordinated to the Au^I atom. Weak Au? Au (d_{Au? Au} = 309 pm) interactions lead to the formation of chains in the crystal of 3 . The trans-anti configuration in 5 can also be assumed for the complexes 6 and 11 for sterical reasons. Compound 1 reacts with K₂[M(dto)₂] (dto = d i t hio o xalato, M = Pd, Pt) to give the expected bis(triphenylphosphinegold) adducts 12 and 13 . Complex 2 , however, affords with dithiooxalato metal dianions the compound [(CO)₅Re]₂(dto)₂ ( 14 ) as final product. (Ph₃PAu)₂dto ( 15 ) is obtained by reaction of 1 with K₂dto. [(CO)₅Re]₂FeNO(dto)₂ ( 16 ) can be isolated as an unstable adduct from the reaction of 2 with [Fe(NO)(dto)₂]^2? Re(CO)₅⁺ and Ph₃PAu⁺ can be added to the bridging S atoms of [(ON)₂Fe(μ-S)₂Fe(NO)₂]^2? to give 17 and 18