Thionitrosylkomplexe des Rutheniums. Die Kristallstruktur von (PPh4)2[{RuBr4(NS)}2(μ-N2S2)]

Thionitrosyl Complexes of Ruthenium. Crystal Structure of (PPh₄)₂[{RuBr₄(NS)}₂ (μ-N₂S₂)] Ruthenium trichloride reacts with trithiazyl chloride, yielding cis-RuCl₄ (NS)₂. With triphenylmethylphosphonium chloride this forms the complex [RuCl₄(NS)₂Cl]^? in which a chloride ion is bonded between the sulfur atoms in a chelate manner. With tetraphenylphosphonium bromide, RuCl₄(NS)₂ undergoes a redox reaction that affords (PPh₄)₂[{RuCl₄(NS)}₂(μ-N₂S₂)] which can be transformed to the title compound by the action of trimethylsilyl bromide. The i.r. spectra are reported. The crystal structure of (PPh₄)₂[{RuBr₄(NS)}₂(μ-N₂S₂)] · 4 CH₂X₂ (X ? Cl, Br) was determined with X-ray diffraction data (1534 observed reflexions, R = 0.085). Crystal data: monoclinic, space group P2₁/n, Z = 2, a = 1680.7, b = 1287.0, c = 1706.1 pm and β = 99.97°. The compound consists of tetraphenylphosphonium cations, CH₂Br₂ and CH₂Cl₂ molecules (statistically) and centrosymmetric anions [{RuBr₄(NS)}₂(μ-N₂S₂)]^2? in which the ruthenium atoms are linked via the nitrogen atoms of a planar N₂S₂ ring. In the corresponding trans-positions every Ru atom has a thionitrosyl ligand with a nearly arrangement Ru?N?S with RuN and NS bond lengths of 169 und 151 pm, respectively. Four bromine atoms complete the distorted octahedral coordination of each ruthenium atom. The bromine atoms that are coplanar with the N₂S₂ ring form rather short Br…?S contacts with a mean distance of 317 pm.     

Koordinativ ungesättigte Dirutheniumkomplexe: Synthese und Kristallstrukturen von [Ru2(CO)n(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (n = 4; 5) und [Ru2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]

Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐ray Crystal Structures of [Ru₂(CO)_n(μ‐H)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] (n = 4; 5) and [Ru₂(CO)₄(μ‐CH₂)(μ‐H)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] The reaction of [Ru₂(μ‐CO)(CO)₅(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 2 ) with dppm yields the dinuclear species [Ru₂(μ‐CO)(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 3 ) (dppm = Ph₂PCH₂PPh₂). Under thermal or photolytic conditions 3 loses very easily one carbonyl ligand and affords the corresponding electronically and coordinatively unsaturated complex [Ru₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 4 ). 4 is also obtainable by an one‐pot synthesis from [Ru₃(CO)₁₂], an excess of ^tBu₂PH and stoichiometric amounts of dppm via the formation of [Ru₂(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)₂] ( 1 ). 4 exhibits a Ru–Ru double bond which could be confirmed by addition of methylene to the dimetallacyclopropane [Ru₂(CO)₄(μ‐CH₂)(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 5 ). The molecular structures of 3 , 4 and 5 were determined by X‐ray crystal structure analyses.     

Koordinativ ungesättigte Dirutheniumkomplexe: Synthese und Kristallstrukturen von [Ru2(CO)4(μ‐H)(μ‐S)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [Ru2(CO)4(μ‐X)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (X = Cl,S2CH)

Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐Ray Crystal Structures of [Ru₂(CO)₄(μ‐H)(μ‐S)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], [Ru₂(CO)₄(μ‐X)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] (X = Cl, S₂CH) [Ru₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 1 ) reacts in benzene with elemental sulfur to the addition product [Ru₂(CO)₄(μ‐H)(μ‐S)(μ‐P^tBu₂)(μ‐dppm)] ( 2 ) (dppm = Ph₂PCH₂PPh₂). 2 is also obtained by reaction of 1 with ethylene sulfide. The reaction of 1 with carbon disulfide yields with insertion of the CS₂ into the Ru₂(μ‐H) bridge the dithioformato complex [Ru₂(CO)₄(μ‐S₂CH)(μ‐P^tBu₂)(μ‐dppm)] ( 3 ). Furthermore, 1 reacts with [NO][BF₄] to the complex salt [Ru₂(CO)₄(μ‐NO)(μ‐H)(μ‐P^tBu₂)(μ‐dppm)][BF₄] ( 4 ), and reaction of 1 with CCl₄ or CHCl₃ affords spontaneously [Ru₂(CO)₄(μ‐Cl)(μ‐P^tBu₂)(μ‐dppm)] ( 5 ) in nearly quantitative yield. The molecular structures of 2 , 3 and 5 were confirmed by crystal structure analyses.     

Neue phosphidoverbrückte Mehrkernkomplexe des Ag und Zn. Die Kristallstrukturen von [Ag3(PPh2)3(PnBu2tBu)3], [Ag4(PPh2)4(PR3)4] (PR3 = PMenPr2, PnPr3), [Ag4(PPh2)4(PEt3)4]n, [Zn4(PPh2)4Cl4(PRR2)2] (PRR′2 = PMenPr2, PnBu3, PEt2Ph), [Zn4(PhPSiMe3)4Cl4(C4H8O)2] und [Zn4(PtBu2)4Cl4]

New Phosphido-bridged Multinuclear Complexes of Ag and Zn. The Crystal Structures of [Ag₃(PPh₂)₃(PⁿBu₂^tBu)₃], [Ag₄(PPh₂)₄(PR₃)₄] (PR₃ = PMeⁿPr₂, PⁿPr₃), [Ag₄(PPh₂)₄(PEt₃)₄]_n, [Zn₄(PPh₂)₄Cl₄(PRR′₂)₂] (PRR′₂ = PMeⁿPr₂, PⁿBu₃, PEt₂Ph), [Zn₄(PhPSiMe₃)₄Cl₄(C₄H₈O)₂] and [Zn₄(P^tBu₂)₄Cl₄] AgCl reacts with Ph₂PSiMe₃ in the presence of tertiary Phosphines (PⁿBu₂^tBu, PMeⁿPr₂, PⁿPr₃ and PEt₃) to form the multinuclear complexes [Ag₃(PPh₂)₃(PⁿBu₂^tBu)₃] 1 , [Ag₄(PPh₂)₄(PR₃)₄] (PR₃ = PMeⁿPr₂ 2 , PⁿPr₃ 3 ) and [Ag₄(PPh₂)₄(PEt₃)₄]_n 4 . In analogy to that ZnCl₂ reacts with Ph₂PSiMe₃ and PRR′₂ to form the multinuclear complexes [Zn₄(PPh₂)₄Cl₄(PRR′₂)₂] (PRR′₂ = PMeⁿPr₂ 5 , PⁿBu₃ 6 , PEt₂Ph 7 ). Further it was possible to obtain the compounds [Zn₄(PhPSiMe₃)₄Cl₄(C₄H₈O)₂] 8 and [Zn₄(P^tBu₂)₄Cl₄] 9 by reaction of ZnCl₂ with PhP(SiMe₃)₂ and ^tBu₂PSiMe₃, respectively. The structures were characterized by X-ray single crystal structure analysis. Crystallographic data see “Inhaltsübersicht”.     

Synthesis and Crystal Structures of the Novel Tetrameric Nitrido Complexes [{cyclo-ReN}4(S2CNEt2)6(MeOH)2(PPh3)2][BPh4]2 · CH2Cl2 · 2 H2O and [{cyclo-ReN}4(S2CNEt2)4Cl4(PMe2Ph)4] · 2 acetone

Novel tetrameric rhenium(V) complexes have been prepared from [ReNCl₂(PPh₃)₂] and [ReN(PMe₂Ph)(S₂CNEt)₂], respectively. [ReNCl₂(PPh₃)₂] reacts with 1.5 equivalents of KS₂CNEt₂ in methanol to yield the unusual dark red species [{cyclo-ReN}₄(S₂CNEt₂)₆(MeOH)₂(PPh₃)₂][BPh₄]₂ · CH₂Cl₂ · 2 H₂O ( 1 ). The crystal structure of the tetramer (triclinic, space group P1, a = 13.842(2), b = 15.213(2), c = 16.796(3) Å, α = 67.88(1), β = 70.90(1), γ = 88.05(1)°, U = 3080.2(8) ų, Z = 1) shows four rhenium atoms in a square configuration which are bridged via linear asymmetric Re≡N–Re groups with bond lengths of about 169 and 203 pm. The molecule contains a centre of symmetry with two distinct octahedral rhenium environments. The first rhenium environment contains two bidentate dithiocarbamate ligands which complete the octahedral geometry and the second contains a bidentate dithiocarbamate ligand, coordinated methanol and has retained a single phosphine coligand. A symmetric compound containing the {cyclo-ReN}₄ core is obtained from the reaction of [ReN(PMe₂Ph)(S₂CNEt₂)₂] with Al₂Cl₆ in acetone. [{cyclo-ReN}₄(S₂CNEt₂)₄Cl₄(PMe₂Ph)₄] · 2 acetone ( 2 ) forms red crystals (monoclinic, space group C2/c, a = 21.432(6), b = 13.700(3), c = 28.060(9) Å, β = 102.37(1)°, U = 8048(4) Å3, Z = 4) with each rhenium atom coordinated by a bidentate dithiocarbamato, a phosphine and a chloro ligand. The non-planar 8-membered {ReN}₄ ring contains asymmetric Re≡N–Re bridges (mean values: 1.69 Å and 2.029 Å, respectively). In contrast, reaction of [ReNCl(S₂CNEt₂)(PMe₂Ph)₂] with one equivalent of K[S₂CN(Me)CH₂CH₂NMe₃]I gave the mixed dithiocarbamato-cation [ReN(S₂CNEt₂)(S₂CN(Me)CH₂CH₂NMe₃)(PMe₂Ph)]⁺ ( 3 ) which was isolated as a tetraphenylborate salt.     

Studien zur CH-aktivierung: II. Der einfluss der liganden auf die bildung von aryl(hydrido)ruthenium(II)- und -osmium(II)-komplexen aus aromaten

The complexes trans-MCl₂(PMe₃)₄ (M = Ru, Os) react with CO and P(OMe)₃ to give the mono- and disubstituted derivatives trans,mer-MCl₂(PMe₃)₃L (L = CO, P(OMe)₃) and all-trans-MCl₂(PMe₃)₂[P(OMe)₃]₂, respectively. On reaction of trans-RuCl₂[P(OMe)₃]₄ with CO and PMe₃, the compounds trans,mer-RuCl₂[P(OMe)₃]₃(CO) and trans,cis,cis-RuCl₂(PMe₃)₂[P(OMe)₃]₂ are synthesized. The reduction of MCl₂(PMe₃)₂[P(OMe)₃]₂ with Na/Hg in benzene or toluene via {M(PMe₃)₂[P(OMe)₃]₂} as an intermediate leads to subsequent intermolecular addition of the arene and to the aryl(hydrido)metal complexes cis,trans,cis-MH(C₆H₅)(PMe₃)₂[P(OMe)₃]₂ (M = Ru, Os) and MH(C₆H₄CH₃)(PMe₃)₂[P(OMe)₃)₂ (M = Os). For M = Ru, in the presence of P(OMe)₃, the ruthenium(0) compound Ru(PMe₃)₂(P(OMe)₃]₃ is formed. The hydrido(phenyl) complexes react with equimolar amounts of Br₂ or I₂ by elimination of benzene to produce the dihalogenometal compounds cis,trans,cis-MX₂(PMe₃)₂[P(OMe)₃]₂. The reaction of trans-RuCl₂(PMe₃)₄ with Na/Hg in the presence of PPh₃ leads to the ortho-metallated complex fac-RuH(η²-C₆H₄PPh₂)(PMe₃)₃, which reacts with CH₃I, CS₂, COS and HCl to give the compounds mer-RuI(η²-C₆H₄PPh₂)(PMe₃)₃, fac-Ru(SCHS)(η²-C₆H₄PPh₂)(PMe₃)₃, fac-Ru(S₂CO)(CO)(PMe₃)₃ and RuCl₂(PMe₃)₃, respectively. The paramagnetic 17-electron complexes [MCl₂(PMe₃)_nL_4-n]PF₆ are obtained on oxidation of MCl₂(PMe₃)_nL_4-n with AgPF₆. Their UV spectra exhibit a characteristic CT band. [RuCl₂(PMe₃)₄]PF₆ and [OsCl₂(PMe₃)₄]PF₆ react with CO and P(OMe)₃ by reduction to form the corresponding ruthenium(II) and osmium(II) compounds MCl₂(PMe₃)_nL_4-n.     

Synthesis and spectroscopic studies of some new metal carbonyl derivatives of 1-(2-pyridylazo)-2-naphthol

Interaction of 1-(2-pyridylazo)-2-naphthol (PAN) with [Mo(CO)₆] in air resulted in formation of the tricarbonyl oxo-complex [Mo(O)(CO)₃(PAN)], 1. The dicarbonyl complex [Ru(CO)₂(PAN)], 3, was obtained from the reaction of [Ru₃(CO)₁₂] with PAN. In presence of triphenyl phosphine (PPh₃), the reaction of PAN with either Mo(CO)₆ or Ru₃(CO)₁₂ gave [Mo(CO)₃(PAN)(PPh₃)], 2, and [Ru(CO)₂(PAN)(PPh₃)], 4. All the complexes were characterized by elemental analysis, mass spectrometry, IR, and NMR spectroscopy. The thermal properties of the complexes were also investigated by thermogravimetry.     

Synthesis and Crystal Structures of the Molybdenum(II) Complexes with the N,N‐dimethylthiocarbamoyl Containing Ligand: Crystal Structures of [Mo(CO)2(η2‐S2COEt)(η2‐SCNMe2)(PPh3)] and [Mo(CO)2(η2‐S2CNC4H8)(η2‐SCNMe2)(PPh3)]

The reaction of the thiocarbamoyl‐molybdenum complex [Mo(CO)₂(η²‐SCNMe₂)(PPh₃)₂Cl] 1 , with EtOCS2K and C4H8NCS2NH4 in dichloromethane at room temperature yielded the seven coordinated ethyldithiocarbonate thiocarbamoyl‐molybdenum complex [Mo(CO)₂(η²‐S₂COEt)(η²‐SCNMe₂)(PPh₃)] 2 , and the dithiocarbamate thiocarbamoyl‐molybdenum complex [Mo(CO)₂(η²‐S₂CNC₄H₈)(η²‐SCNMe₂)(PPh₃)] 3 . The geometry around the metal atom of compounds 2 and 3 are capped octahedrons as revealed by X‐ray diffraction analyses. The thiocarbamoyl and ethyldithiocarbonate or pyrrolidinyldithiocarbamate ligands coordinate to the molybdenum metal center through the carbon and sulfur and two sulfur atoms, respectively. Structure parameters, NMR, IR and Mass spectra are in agreement with the crystal chemistry of the two compounds.     

Addition von kationischen Lewis‐Säuren [M′Ln]+ (M′Ln = Fe(CO)2Cp,Fe(CO)(PPh3)Cp,Ru(PPh3)2Cp,Re(CO)5, ${1 \over 2}$ Pt(PPh3)2, W(CO)3Cp an die anionischen Thiocarbonyl‐Komplexe [HB(pz)3(OC)2M(CS)]− (M = Mo,W; pz = 3,5‐dimethylpyrazol‐1‐yl)

Addition of Cationic Lewis Acids [M′L_n]⁺ (M′L_n = Fe(CO)₂Cp, Fe(CO)(PPh₃)Cp, Ru(PPh₃)₂Cp, Re(CO)₅, Pt(PPh₃)₂, W(CO)₃Cp to the Anionic Thiocarbonyl Complexes [HB(pz)₃(OC)₂M(CS)]⁻ (M = Mo, W; pz = 3,5‐dimethylpyrazol‐1‐yl) Adducts from Organometallic Lewis Acids [Fe(CO)₂Cp]⁺, [Fe(CO)(PPh₃)Cp]⁺, [Ru(PPh₃)₂Cp]⁺, [Re(CO)₅]⁺, [ Pt(PPh₃)₂]⁺, [W(CO)₃Cp]⁺ and the anionic thiocarbonyl complexes [HB(pz)₃(OC)₂M(CS)]⁻ (M = Mo, W) have been prepared. Their spectroscopic data indicate that the addition of the cations occurs at the sulphur atom to give end‐to‐end thiocarbonyl bridged complexes [HB(pz)₃(OC)₂MCSM′L_n].     

Reaktionen von Zinnchloriden mit Polysulfiden. Die Kristallstrukturen von (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O] und (PPh4)2[SnCl6] · S8 · 2CH3CN

Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh₄)₂[SnCl₂(S₆)₂], (PPh₄)₂[Sn₄Cl₄S₅(S₃)O], and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN . The reaction of PPh₄[SnCl₃] with Na₂S₄ in acetonitrile in the presence of small amounts of water yields (PPh₄)₂[Sn₄Cl₄S₅(S₃)O] and minor amounts of (PPh₄)₂[SnCl₂(S₆)₂], PPh₄Cl · 2S₈ and (PPh₄)₂[SnCl₆]. SnCl₄ is partially reduced by (PPh₄)₂S_x, PPh₄[SnCl₃] and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN being produced. According to the X-ray crystal structure determination the [Sn₄Cl₄S₅(S₃)O]^2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S₃ group. In the [SnCl₂(S₆)₂]^2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S₆ groups. Octahedral [SnCl₆]^2? ions and S₈ molecules in the crown conformation are present in (PPh₄)₄[SnCl₆] · S₈ · 2CH₃CN.     

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.     

Binding H2, N2, H-, and BH3 to transition-metal sulfur sites: synthesis and properties of [RuL(PR3)(N2Me2S2)] Complexes (L=eta2-H2, H-, BH3; R=Cy, iPr)

The reactions of [Ru(N₂)(PR₃)(‘N₂Me₂S₂’)] [‘N₂Me₂S₂’=1,2‐ethanediamine‐N,N′‐dimethyl‐N,N′‐bis(2‐benzenethiolate)(2?)] [ 1 a (R=iPr), 1 b (R=Cy)] and [μ‐N₂{Ru(N₂)(PiPr₃)(‘N₂Me₂S₂’)}₂] ( 1 c ) with H₂, NaBH₄, and NBu₄BH₄, intended to reduce the N₂ ligands, led to substitution of N₂ and formation of the new complexes [Ru(H₂)(PR₃)(‘N₂Me₂S₂’)] [ 2 a (R=iPr), 2 b (R=Cy)], [Ru(BH₃)(PR₃)(‘N₂Me₂S₂’)] [ 3 a (R=iPr), 3 b (R=Cy)], and [Ru(H)(PR₃)(‘N₂Me₂S₂’)]^? [ 4 a (R=iPr), 4 b (R=Cy)]. The BH₃ and hydride complexes 3 a , 3 b , 4 a , and 4 b were obtained subsequently by rational synthesis from 1 a or 1 b and BH₃?THF or LiBEt₃H. The primary step in all reactions probably is the dissociation of N₂ from the N₂ complexes to give coordinatively unsaturated [Ru(PR₃)(‘N₂Me₂S₂’)] fragments that add H₂, BH₄^?, BH₃, or H^?. All complexes were completely characterized by elemental analysis and common spectroscopic methods. The molecular structures of [Ru(H₂)(PR₃)(‘N₂Me₂S₂’)] [ 2 a (R=iPr), 2 b (R=Cy)], [Ru(BH₃)(PiPr₃)(‘N₂Me₂S₂’)] ( 3 a ), [Li(THF)₂][Ru(H)(PiPr₃)(‘N₂Me₂S₂’)] ([Li(THF)₂]‐ 4 a ), and NBu₄[Ru(H)(PCy₃)(‘N₂Me₂S₂’)] (NBu₄‐ 4 b ) were determined by X‐ray crystal structure analysis. Measurements of the NMR relaxation time T₁ corroborated the η² bonding mode of the H₂ ligands in 2 a (T₁=35 ms) and 2 b (T₁=21 ms). The H,D coupling constants of the analogous HD complexes HD‐ 2 a (¹J(H,D)=26.0 Hz) and HD‐ 2 b (¹J(H,D)=25.9 Hz) enabled calculation of the H? D distances, which agreed with the values found by X‐ray crystal structure analysis ( 2 a : 92 pm (X‐ray) versus 98 pm (calculated), 2 b : 99 versus 98 pm). The BH₃ entities in 3 a and 3 b bind to one thiolate donor of the [Ru(PR₃)(‘N₂Me₂S₂’)] fragment and through a B‐H‐Ru bond to the Ru center. The hydride complex anions 4 a and 4 b are extremely Brønsted basic and are instantanously protonated to give the η²‐H₂ complexes 2 a and 2 b .     

Koordinativ ungesättigte Dieisenkomplexe: Synthese und Kristallstrukturen von [Fe2(CO)4(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [Fe2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]

Coordinatively Unsaturated Diiron Complexes: Synthesis and Crystal Structures of [Fe₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] and [Fe₂(CO)₄(μ‐CH₂)(μ‐H)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] [Fe₂(μ‐CO)(CO)₆(μ‐H)(μ‐P^tBu₂)] ( 1 ) reacts spontaneously with dppm (dppm = Ph₂PCH₂PPh₂) to give [Fe₂(μ‐CO)(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 2 c ). By thermolysis or photolysis, 2 c loses very easily one carbonyl ligand and yields the corresponding electronically and coordinatively unsaturated complex [Fe₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 3 ). 3 exhibits a Fe–Fe double bond which could be confirmed by the addition of methylene to the corresponding dimetallacyclopropane [Fe₂(CO)₄(μ‐CH₂)(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 4 ). The reaction of 1 with dppe (Ph₂PC₂H₄PPh₂) affords [Fe₂(μ‐CO)(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppe)] ( 5 ). In contrast to the thermolysis of 2 c , yielding 3 , the heating of 5 in toluene leads rapidly to complete decomposition. The reaction of 1 with PPh₃ yields [Fe₂(CO)₆(H)(μ‐P^tBu₂)(PPh₃)] ( 6 a ), while with ^tBu₂PH the compound [Fe₂(μ‐CO)(CO)₅(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 6 b ) is formed. The thermolysis of 6 b affords [Fe₂(CO)₅(μ‐P^tBu₂)₂] and the degradation products [Fe(CO)₃(^tBu₂PH)₂] and [Fe(CO)₄(^tBu₂PH)]. The molecular structures of 3 , 4 and 6 b were determined by X‐ray crystal structure analyses.     

Preparation and Characterization of an Unusual Di-Cobalt Complex; X-Ray Crystal Structure of Co(CO)2(μ-CO)(μ:η2,η4-C4Ph4)Co(CO)2(PPh3)

Reaction of [MoCo(CO)₅(PPh₃)₂(η⁵-C₅H₅)] (1) with diphenylacetylene in tetrahydrofuran at 50 °C yielded two heterobimetallic compounds, [MoCo(CO)₄.(PPh₃){μ-PhC ? CPh}(η⁵-C₅H₅)] (4) and [MoCo(CO)₅{μ-PhC ? CPh} (η⁵-C₅H₅)] (5). However, an unexpected product, Co(CO)₂(μ-CO)(μ:η₂,η⁴-C₄Ph₄)Co(CO)₂(PPh₃) (6), was observed while attempting to grow the crystals for structural determination of 4. The X-ray crystal structure of 6 was determined: triclinic, $ {\rm P}\bar 1 $, a = 11.654(2) Å, b = 12.864(2) Å, c = 13.854(2) Å, α = 89.67(2)°, β = 86.00(2)°, γ= 83.33(2)°, V = 2057.9(6) ų Z=2. In 6, two cobalt fragments are at apical and basal positions of the pseudo-pentagonal pyramidal structure, respectively. The electron count for the apical cobalt fragments is 20, which is rather unusual. It is believed that 6 was formed after the fragmentation and recombination of the fragmented species of 4.     

Übergangsmetallkomplexe mit schwefelliganden: XX. Ruthenium(II)-CO- und phosphinkomplexe mit [Ru(SNNS)]- fragmenten,die die vierzähnigen thiolat-amin-liganden bmae2− bzw. bmab2− enthalten [bmae2−= 1,2-bis(2-mercaptoanilino)-ethan(−2); bmab2− = 2,3-bis(2-mercaptoanilino)butan(−2)]

In order to compare the influence of thiolate amine and thiolate thioether ligands on the reactivity of Ru^II centers, the complexes [Ru(bmae)] and [Ru(bmab)] have been synthesized. These are isoelectronic to [Ru(dttd)] complexes [bmae²⁻ = 1,2-bis(2-mercapto-anilino)ethane(−2); bmab²⁻ = 2,3-bis(2-mercapto-anilino)butane(−2); dttd²⁻ = 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane(−2)]. The complexes [Ru(CO)₃ (THF)Cl₂], [Ru(PMe₃)₄Cl₂] and [Ru(PPh₃)₂ (CH₃CN)₂Cl₂] are treated with bmae-Na₂ or bmab-Na₂ to give the compounds [RuL₂ (bmae)] and [RuL₂ (bmab)] respectively (L  CO, PMe₃, PPh₃). These complexes are generally less reactive than the corresponding [RuL₂(dttd)] compounds. UV photolysis of [Ru(CO)₂ (bmae)] in the presence of PMe₃ yields [Ru(CO)PMe₃ (bmae)]; the bmae ligand proves to be photostable. In contrast to the substitution-labile [Ru(PPh₃)₂-dttd], the bmae complex [Ru(PPh₃)₂ (bmae)] proves to be substitution-inert. Since the X-ray structure analysis yields no hints of structural anomalies for [Ru(PPh₃)₂ (bmae)], electronic reasons might cause the different substitution behaviour of [Ru(PPh₃)₂ (bmae)] and [Ru(PPh₃)₂dttd].The stabilization of five-coordinate intermediates by the π-donor properties of the sulfur donor atoms should be better in the case of [Ru(PPh₃)dttd] than in the case of [Ru(PPh₃)(bmae)].     

Synthesis,Characterization, and X‐ray Structures of Ru3(CO)9(dotpm)(L) Complexes [L = PPh3, P(C6H4Cl‐p)3, and PPh2(C6H4Br‐p)]

The reaction of Ru₃(CO)₁₀(dotpm) ( 1 ) [dotpm = (bis(di‐ortho‐tolylphosphanyl)methane)] and one equivalent of L [L = PPh₃, P(C₆H₄Cl‐p)₃ and PPh₂(C₆H₄Br‐p)] in refluxing n‐hexane afforded a series of derivatives [Ru₃(CO)₉(dotpm)L] ( 2 – 4 ), respectively, in ca. 67–70 % yield. Complexes 2 – 4 were characterized by elemental analysis (CHN), IR, ¹H NMR, ¹³C{¹H} NMR and ³¹P{¹H} NMR spectroscopy. The molecular structures of 2 , 3 , and 4 were established by single‐crystal X‐ray diffraction. The bidentate dotpm and monodentate phosphine ligands occupy equatorial positions with respect to the Ru triangle. The effect of substitution resulted in significant differences in the Ru–Ru and Ru–P bond lengths.     

Coordination chemistry of the [Pt2(μ-S)2(PPh3)4] metalloligand with π-hydrocarbon derivatives of d ruthenium(II), osmium(II), rhodium(III) and iridium(III)

The reactivity of [Pt₂(μ-S)₂(PPh₃)₄] towards [RuCl₂(η⁶-arene)]₂ (arene=C₆H₆, C₆Me₆, p-MeC₆H₄Prⁱ=p-cymene), [OsCl₂(η⁶-p-cymene)]₂ and [MCl₂(η⁵-C₅Me₅)]₂ (M=Rh, Ir) have been probed using electrospray ionisation mass spectrometry. In all cases, dicationic products of the type [Pt₂(μ-S)₂(PPh₃)₄ML]²⁺ (L=π-hydrocarbon ligand) are observed, and a number of complexes have been prepared on the synthetic scale, isolated as their BPh₄⁻ or PF₆⁻ salts, and fully characterised. A single-crystal X-ray structure determination on the Ru p-cymene derivative confirms the presence of a pseudo-five-coordinate Ru centre. This resists addition of small donor ligands such as CO and pyridine. The reaction of [Pt₂(μ-S)₂(PPh₃)₄] with RuClCp(PPh₃)₂ (Cp=η⁵-C₅H₅) gives [Pt₂(μ-S)₂(PPh₃)₄RuCp]⁺. In addition, the reaction of [Pt₂(μ-S)₂(PPh₃)₄] with the related carbonyl complex [RuCl₂(CO)₃]₂, monitored by electrospray mass spectrometry, gives [Pt₂(μ-S)₂(PPh₃)₄Ru(CO)₃Cl]⁺.     

Aktivierung von Schwefelkohlenstoff an Trirutheniumclustern: Synthese und Kristallstruktur von [Ru3(CO)4(μ‐PCy2)2(μ‐Ph2PCH2PPh2)(μ3‐S){μ3‐η2‐CSC(S)S}]

Activation of Carbon Disulfide on Triruthenium Clusters: Synthesis and X‐Ray Crystal Structure Analysis of [Ru₃(CO)₄(μ‐PCy₂)₂(μ‐Ph₂PCH₂PPh₂)(μ₃‐S){μ₃‐η²‐CSC(S)S}] [Ru₃(CO)₄(μ‐H)₃(μ‐PCy₂)₃(μ‐dppm)] ( 2 ) (dppm = Ph₂PCH₂PPh₂) reacts with CS₂ at room temperature and yields the open 50 valence electron cluster [Ru₃(CO)₄(μ‐PCy₂)₂(μ‐dppm)(μ₃‐S){μ₃‐η²‐CSC(S)S}] ( 3 ) containing the unusual μ₃‐η²‐C₂S₃ mercaptocarbyne ligand. Compound 3 was characterized by single crystal X‐ray structure analysis.     

Reaktionen an komplexgebundenen liganden : XXXIII. Synthese,reaktivität und struktur von eisen-carbonyl-komplexen mit vierzähnigen thioäther-thiolato-liganden

The reaction of the anion [Fe(CO)₂(S₂C₆H₄)₂]^2? with 1,2-C₂H₄Br₂ yields [Fe(CO)₂(dttd)] containing the dianion of the new tetradentate thioether-thiol ligand 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecan (dttd-H₂). Iron(II) salts coordinate CO under normal conditions also in the presence of alkyl mercaptides; the reaction of, e.g., Fe²⁺, 1,2-S₂C₂H₄^2? and CO yields [Fe(CO)₂(S₂C₂H₄)]^2? which reacts with 1,2-C₂H₄Br₂ analogously yielding [Fe(CO)₂(tdd)], (ttd = [1,4,7,10-tetrathiadecane]^2?). As shown by X-ray analysis the iron centre in [Fe(CO)₂(ttd)] is coordinated pseudo-octahedrally by four sulfur atoms and two cis-carbonyl groups. [Fe(CO)₂(dttd)] splits off one CO ligand upon heating in THF yielding [Fe(CO)(dttd)], which on reaction with PMe₃ yields [Fe(CO)(PMe₃)(dttd)]. The new complexes are characterized by elemental analyses as well as by IR, ¹H NMR and mass spectroscopy.     

RuS4Cl12 und Ru2S6Cl16, zwei neue Ruthenium(II)‐Komplexe mit SCl2‐Liganden

RuS₄Cl₁₂ and Ru₂S₆Cl₁₆, Two New Ruthenium(II) Complexes with SCl₂ Ligands Ru powder was reacted with SCl₂ in closed silika ampoules at 140 °C. From the black solution three compounds RuS₄Cl₁₂ 1 , Ru₂S₆Cl₁₆ 2 , and Ru₂S₄Cl₁₃ 3 could be crystallized and characterized by x ray analysis. Black crystals of 1 (monoclinic, a = 9.853(1) Å, b = 11.63(1) Å, c = 15.495(1) Å, β = 105.23(1)°, space group P2₁/c, z = 4) are identified as Trichlorsulfonium‐tris(dichlorsulfan)trichloro‐ruthenat(II) SCl₃[RuCl₃(SCl₂)₃]. In the structure the complex anions fac‐[RuCl₃(SCl₂)₃]^– and the cations [SCl₃]⁺ are connected to ion pairs by three chlorine bridges. The brown crystals of 2 (triclinic, a = 7.754(2) Å, b = 7.997(2) Å, c = 10.708(2) Å, α = 103.74(3)°, β = 98.44(3)°, γ = 108.58(3)°, space group P‐1, z = 1) contain the binuclear complex Bis‐μ‐chloro‐dichloro‐hexakis(dichlorsulfan)‐diruthenium(II), (SCl₂)₃ClRu(μ‐Cl)₂RuCl(SCl₂)₃ with two fac‐RuCl₃(SCl₂)₃‐units connected by two chlorine bridges. 3 was identifyed as a known mixed valence Ru(II,III) binuclear complex [Cl₂(SCl₂)Ru(μ‐Cl)₃Ru(SCl₂)₃]. The vibrational spectra and the thermal behaviour of the compounds are discussed.