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.     

[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.     

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.     

(Carbonyl)Iron‐Selenolates: New Synthetic Methods and Reactions with Electrophiles. Crystal Structures of [(CO)6Fe2(μ‐SeR)2]; R = Me3SiCH2 and p‐O2NC6H4CH2, {(CO)6Fe2[μ‐η2‐Se,Se′‐o‐(SeCH2C6H4CH2Se)]}, and [(CO)6Fe2(μ‐SeFe(CO)2cp)2]

The reactions of Fe(CO)₅ or Fe₃(CO)₁₂ with NaBEt₃H or KB[CH(CH₃)C₂H₅]₃H, respectively and treatment of the resulting carbonylates M₂Fe(CO)₄, M = Na, K with elemental selenium in appropriate ratios lead to the formation of M₂[Fe₂(CO)₆(μ‐Se)₂]. Subsequent reactions with organo halides or the complex fragment cpFe(CO)₂⁺, cp = η⁵‐C₅H₅ afforded the selenolato complexes [Fe₂(CO)₆(μ‐SeR)₂], R = CH₂SiMe₃ ( 1 ), CH₂Ph ( 2 ), p‐CH₂C₆H₄NO₂ ( 3 ), o‐CH₂C₆H₄CH₂ ( 4 ) and cpFe(CO)₂⁺ ( 5 ) in moderate to good yields. A similar reaction employing Ru₃(CO)₁₂, Se and p‐O₂NC₆H₄CH₂Br leads to the formation of the corresponding organic diselenide. The X‐ray structures of 1 , 3 , 4 and 5 were determined and revealed butterfly structures of the Fe₂Se₂ cores. The substituents in 1 , 3  and 5 adopt different conformations depending on their steric demand. In 4 , the conformation is fixed because of the chelate effect of the ligand. The Fe–Se bond lengths lie in the range 235 to 240 pm, with corresponding Fe–Fe bond lengths of 254 to 256 pm. The ⁷⁷Se NMR data of the new complexes are discussed and compared with the corresponding data of related complexes.     

Heterodinukleare Komplexe: Synthese und Kristallstrukturen von [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)]

Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)], [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], and [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] [Ru₃Rh(CO)₇(μ₃‐H)(μ‐P^tBu₂)₂(^tBu₂PH)(μ‐Cl)₂] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) ų. The reaction of 4 with dppm (Ph₂PCH₂PPh₂) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 ų. Moreover single crystals of [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P2₁/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) ų.     

Heteronuclear Nickel‐Iron Complexes and the Crystal Structure of [Fe2(CO)6(μ3‐S)2{Ni(dppe)}]

A series of heteronuclear nickel‐iron complexes [Fe₂(CO)₆(μ‐SH)(μ₃‐S){NiCl(PPh₃)₂}] ( 1 ), [Fe₂(CO)₆(μ‐SH)(μ₃‐S){NiCl(dppe)}] ( 2 ), [Fe₂(CO)₆(μ₃‐S)₂{Ni(PPh₃)₂}] ( 3 ), [Fe₂(CO)₆(μ₃‐S)₂{Ni(dppe)}] ( 4 ) and [Fe₂(CO)₆(μ‐SPh)(μ₃‐S){NiCl(dppe)}] ( 5 ) have been prepared. The structure of 4 has been determined by X‐ray crystallography. The central metal‐sulfur core of 4 has a trigonal bipyramidal shape with a NiFe₂ base plane with two axial sulfur atoms. Each iron atom is 5‐coordinate forming a distorted square pyramid; the nickel is square planar coordinated by two sulfur atoms and two phosphorus atoms.     

Synthesen und NMR‐Untersuchungen von Salzen mit den neuen Anionen [PtXn(CF3)6‐n]2— (n = 0 ‐ 5, X = F,OH, Cl,CN) und die Kristallstrukturanalyse von K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O

Syntheses and NMR Spectroscopic Ivestigations of Salts containing the Novel Anions [PtX_n(CF₃)_6‐n]^2— (n = 0 ‐ 5, X = F, OH, Cl, CN) and Crystal Structure of K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O The first syntheses of trifluoromethyl‐complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K₂[Pt(CN)₄], and hexacyanoplatinates(IV), K₂[Pt(CN)₆], with ClF in anhydrous HF leads after working up of the products to K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O. The structure of the salt is determined by a X‐ray structure analysis, P2₁/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R₁ = 0.0326 (I > 2σ(I)). The reaction of [Bu₄N]₂[Pt(CN)₄] with ClF in CH₂Cl₂ generates mainly cis‐[Bu₄N]₂[PtCl₂(CF₃)₄] and fac‐[Bu₄N]₂[PtCl₃(CF₃)₃], but in contrast that of [Bu₄N]₂[Pt(CN)₆] with ClF in CH₂Cl₂ results cis‐[Bu₄N]₂[PtX₂(CF₃)₄], [Bu₄N]₂[PtX(CF₃)₅] (X = F, Cl) and [Bu₄N]₂[Pt(CF₃)₆]. In the products [Bu₄N]₂[PtX_n(CF₃)_6‐n] (X = F, Cl, n = 0—3) it is possibel to exchange the fluoro‐ligands into chloro‐ and cyano‐ligands by treatment with (CH₃)₃SiCl und (CH₃)₃SiCN at 50 °C. With continuing warming the trifluoromethyl‐ligands are exchanged by chloro‐ and cyano‐ligands, while as intermediates CF₂Cl and CF₂CN ligands are formed. The identity of the new trifluoromethyl‐platinates is proved by ¹⁹⁵Pt‐ and ¹⁹F‐NMR‐spectroscopy.     

Formation of Unusual Complexes from the Reaction of [C(NMe2)3][(CO)4Fe{C(O)NMe2}] with InMe3; Crystal Structures of [C(NMe2)3]3[Fe2(CO)6(μ‐CO){μ‐InFe(CO)4(μ‐O2CNMe2)InFe(CO)4}] and [C(NMe2)3]2[{(CO)4Fe}2In(O2CNMe2)]·THF

The carbamoyl complex [C(NMe₂)₃][(CO)₄Fe{C(O)NMe₂}] ( 1 ) reacts with InMe₃ under loss of the methyl groups to produce a variety of compounds from which only the anionic cluster complexes [C(NMe₂)₃]₃[Fe₂(CO)₆(μ‐CO){μ‐InFe(CO)₄(μ‐O₂CNMe₂)InFe(CO)₄}] ([C N ₃]₃[ 2 ]) and [C(NMe₂)₃]₂[{(CO)₄Fe}₂In(O₂CNMe₂)]·THF ([C N ₃]₂[ 3 ]·THF) could be crystallized and characterized by X‐ray analyses. The anion [ 2 ]^3? has a Fe₂(CO)₉‐like structure and both anions contain the carbaminato ligand either in a bridging or in a chelating function.     

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.     

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.     

Chelating and Tellurolate Ligand‐Transfer Studies of the Complex fac‐[Fe(CO)3(TePh)3]−: Crystal Structures of Heterodinuclear (CO)3Mn(μ‐TePh)3Fe(CO)3 and CpNi(TePh)(PPh3)

Complex fac‐[Fe(CO)₃(TePh)₃]^? was employed as a “metallo chelating” ligand to synthesize the neutral (CO)₃Mn(μ‐TePh)₃Fe(CO)₃ obtained in a one‐step synthesis by treating fac‐[Fe(CO)₃(TePh)₃]^? with fac‐[Mn‐(CO)₃(CH₃CN)₃]⁺. It seems reasonable to conclude that the d⁶ Fe(II) [(CO)₃Fe(TePh)₃]^? fragment is isolobal with the d⁶ Mn(I) [(CO)₃Mn(TePh)₃]^2? fragment in complex (CO)₃Mn(μ‐TePh)₃Fe(CO)₃. Addition of fac‐[Fe(CO)₃(TePh)₃]^? to the CpNi(I)(PPh₃) in THF resulted in formation of the neutral CpNi(TePh)(PPh₃) also obtained from reaction of CpNi(I)(PPh₃) and [Na][TePh] in MeOH. This investigation shows that fac‐[Fe(CO)₃(TePh)₃]^? serves as a tridentate metallo ligand and tellurolate ligand‐transfer reagent. The study also indicated that the fac‐[Fe(CO)₃(SePh)₃]^? may serve as a better tridentate metallo ligand and chalcogenolate ligand‐transfer reagent than fac‐[Fe(CO)₃(TePh)₃]^? in the syntheses of heterometallic chalcogenolate complexes.     

Koordinativ ungesättigte Dirutheniumkomplexe: Synthese und Kristallstrukturen von [Ru2(CO)3L(μ‐η1 : η2‐C≡CPh)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (L = CO,PnBu3)

Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐ray Crystal Structures of [Ru₂(CO)₃L(μ‐η¹ : η²‐C≡CPh)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] (L = CO, PⁿBu₃) [Ru₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 1 ) reacts with several phosphines (L) in refluxing toluene under substitution of one carbonyl ligand and yields the compounds [Ru₂(CO)₃L(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] (L = PⁿBu₃, 2 a ; L = PCy₂H, 2 b ; L = dppm‐P, 2 c ; dppm = Ph₂PCH₂PPh₂). The reactivity of 1 as well as the activated complexes 2 a – c towards phenylethyne was studied. Thus 1 , 2 a and 2 b , respectively, react with PhC≡CH in refluxing toluene with elimination of dihydrogen to the acetylide‐bridged complexes [Ru₂(CO)₄(μ‐η¹ : η²‐C≡CPh)(μ‐P^tBu₂)(μ‐dppm)] ( 3 ) and [Ru₂(CO)₃L(μ‐η¹ : η²‐C≡CPh)(μ‐P^tBu₂)(μ‐dppm)] ( 4 a and 4 b ). The molecular structures of 3 and 4 a were determined by crystal structure analyses.     

On the Reaction of [(CO)3Fe(μ‐Me2NCO)2Fe(CO)2(NHMe2)] with Chelating Ligands — X‐Ray Structures of New Binuclear μ‐Carbamoyl Complexes

Reaction of the binuclear μ‐carbamoyl complex [(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)₂(HNMe₂)] ( 1 ) in toluene with the chelating ligands Ph₂PCH₂PPh₂ (dppm) and Ph₂PCH₂CH₂PPh₂ (dppe) gives different results. With dppm only the complex [(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)₂(dppm)] ( 3 ) with a dangling ligand is obtained under replacement of amine, whereas with dppe depending on the reaction conditions up to three compounds are found. A 1 : 1 mixture of the educts generates the related complex [(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)₂(dppe)] ( 4 ) together with the tetranuclear complex [{(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)₂}₂(dppe)] (5 ). 4 slowly converts into [(CO)₃Fe(μ‐Me₂NCO)₂Fe(CO)(dppe)] ( 6 ) with dppe acting as a chelating ligand. 6 is the first compound in this series in which one of the five CO groups is replaced by another donor. A 2 : 1 molar ratio of 1 and dppe quantitatively produces 5 . Addition of CO to a solution of 6 proceeds under slow reversible conversion of the complex into 4 . The compounds were characterized by the usual spectroscopic methods; 3 , 5 and 6 were also studied by X‐ray diffraction analyses.     

Aktivierung von Schwefelkohlenstoff an Trirutheniumclustern: Synthese und Kristallstruktur von [Ru3(CO)5(μ‐H)2(μ‐PCy2)(μ‐Ph2PCH2PPh2){μ‐η2‐PCy2C(S)}(μ3‐S)] und [Ru3(CO)5(CS)(μ‐H)(μ‐PtBu2)(μ‐PCy2)2(μ3‐S)]

Activation of Carbon Disulfide on Triruthenium Clusters: Synthesis and X‐Ray Crystal Structure Analysis of [Ru₃(CO)₅(μ‐H)₂(μ‐PCy₂)(μ‐Ph₂PCH₂PPh₂){μ‐η²‐PCy₂C(S)}(μ₃‐S)] and [Ru₃(CO)₅(CS)(μ‐H)(μ‐P^tBu₂)(μ‐PCy₂)₂(μ₃‐S)] [Ru₃(CO)₆(μ‐H)₂(μ‐PCy₂)₂(μ‐dppm)] ( 1 ) (dppm = Ph₂PCH₂PPh₂) reacts under mild conditions with CS₂ and yields by oxidative decarbonylation and insertion of CS into one phosphido bridge the opened 50 VE‐cluster [Ru₃(CO)₅(μ‐H)₂(μ‐PCy₂)(μ‐dppm){μ‐η²‐PCy₂C(S)}(μ₃‐S)] ( 2 ) with only two M–M bonds. The compound 2 crystallizes in the triclinic space group P 1 with a = 19.093(3), b = 12.2883(12), c = 20.098(3) Å; α = 84.65(3), β = 77.21(3), γ = 81.87(3)° and V = 2790.7(11) ų. The reaction of [Ru₃(CO)₇(μ‐H)(μ‐P^tBu₂)(μ‐PCy₂)₂] ( 3 ) with CS₂ in refluxing toluene affords the 50 VE‐cluster [Ru₃(CO)₅(CS)(μ‐H)(μ‐P^tBu₂)(μ‐PCy₂)₂(μ₃‐S)] ( 4 ). The compound cristallizes in the monoclinic space group P 2₁/a with a = 19.093(3), b = 12.2883(12), c = 20.098(3) Å; β = 104.223(16)° and V = 4570.9(10) ų. Although in the solid state structure one elongated Ru–Ru bond has been found the complex 4 can be considered by means of the ³¹P‐NMR data as an electron‐rich metal cluster.     

(PPh4)2[(SN)ReCl3(μ‐N)(μ‐NSN)ReCl3(THF)] – ein Nitrido‐Thionitrosyl‐Dinitridosulfato‐Komplex des Rheniums

(PPh₄)₂[(SN)ReCl₃(μ‐N)(μ‐NSN)ReCl₃(THF)] – a Nitrido‐Thionitrosyl‐Dinitridosulfato‐Complex of Rhenium The title compound has been prepared from PPh₄[Re^VIICl₄(NSCl)₂] with excess N(SiMe₃)₃ in dichloromethane solution to give red‐brown single crystals after recrystallisation from acetonitrile/THF solutions. As a by‐product PPh₄[ReNCl₄] is formed. (PPh₄)₂[(SN)ReCl₃(μ‐N)(μ‐NSN)ReCl₃(THF)] ( 1 ): Space group P2₁/n, Z = 4, lattice dimensions at –80 °C: a = 1024.1(1), b = 2350.2(1), c = 2315.4(2) pm, β = 94.09(1)°, R₁ = 0.0403. In the complex anion of 1 the rhenium atoms are connected by an asymmetric Re≡N–Re bridge as well as by a (NSN)^4–‐bridge to form a planar Re₂N(NSN) six‐membered heterocycle. Both rhenium atoms are coordinated by three chlorine atoms, one of them by a thionitrosyl ligand, the other one by the oxygen atom of a thf molecule.     

Clusterkomplexe [M2Rh(μ‐PCy2)(μ‐CO)2(CO)8] mit triangularem Metallgerüst RhM2 (M = Mn,Re; M2 = MnRe): Synthese,Struktur, Ringöffnungen und Katalysatoreigenschaften für die Isomerisierung und Hydroformylierung von 1‐Hexen

Cluster Complexes [M₂Rh(μ‐PCy₂)(μ‐CO)₂(CO)₈] with Triangular Core of RhM₂ (M = Re, Mn; M₂ = MnRe): Synthesis, Structure, Ring Opening Reaction, and Properties as Catalysts for Hydroformylation and Isomerisation of 1‐Hexene The salts PPh₄[M₂(μ‐H)(μ‐PCy₂)(CO)₈] and Rh(COD)[ClO₄] were in equimolar amounts reacted at –40 to –15 °C in the presence of CO_(g) in CH₂Cl₂/methanol solution under release of PPh₄[ClO₄] to intermediates. Such species formed in a selective reaction the unifold unsaturated 46 valence electrons title compounds [M₂Rh(μ‐PCy₂)(μ‐CO)₂(CO)₈] (M = Re 1 , Mn 2 ; M₂ = MnRe 3 ) in yields of > 90%; analogeous the derivatives with the PPh₂ bridge could the obtained (M = Re 4 , Mn 5 ). From these clusters the molecular structure of 2 was determined by a single crystal X‐ray analysis. The exchange of the labil CO ligand attached at the rhodium ring atom in 1 – 3 against selected tertiary and secondary phosphanes in solution gave the substitution products [M₂RhL(μ‐PCy₂)(μ‐CO)₂(CO)₇] (M = Re: L = PMe₃ 6 , P(n‐Bu)₃ 7 , P(n‐C₆H₄SO₃Na)₃ 8 , HPCy₂ 9 , HPPh₂ 10 , HPMen₂ 11 , M₂ = MnRe: L = HPCy₂ 12 ) nearly quantitative. Such dimanganese rhodium intermediates ligated with secondary phosphanes were converted in a subsequent reaction to the ring‐opened complexes [MnRh(μ‐PCy₂)(μ‐H)(CO)₅Mn(μ‐PR₂)(CO)₄] (M = Mn: R = Cy 13 , Ph 14 , Mn 15 ). The molecular structure of 13 , which showed in the time scale of the ³¹P NMR method a fluxional behaviour, was determined by X‐ray structure analysis. All products obtained were always characterized by means of υ(CO)Ir, ¹H and ³¹P NMR measurements. From the reactants of hydroformylation process, CO_(g) 1 – 2 in different solvents afforded at 20 °C under a reversible ring opening reaction the valence‐saturated complexes [MRh(μ‐PCy₂)(CO)₇M(CO)₅] (M = Re 16 , Mn 17 ), whereas the reaction of CO_(g) and the ring‐opened 13 to [MnRh(μ‐PCy₂)(μ‐H)(CO)₆Mn(μ‐PCy₂)(CO)₄] ( 18 ) was as well reversible. The molecular structures of 17 and 18 were determined by X‐ray analysis. The υ(CO)IR, ¹H and ³¹P NMR measurements in pressure‐resistant reaction vessels at 20 °C ascertained the heterolytic splitting of hydrogen in the reaction of 1 – 2 dissolved in CDCl₃ or THF‐d₈ under formation of product monoanions [M₂Rh(μ‐CO)(μ‐H)(μ‐PCy₂)(CO)₉]^– (M = Re, Mn), which also were formed by the reaction of NaBH₄ and 1 – 2 . Finally, the substrate 1‐hexene and 1 and 3 gave under the release of the labil CO ligand an η²‐coordination pattern of hexene, which was weekened going from the Re to the Mn neighbor atoms. After the results of the catalytic experiments with 1 and 2 as catalysts, such change in the bonding property revealed an advantageous formation of hydroformylation products for the dirhenium rhodium catalyst 1 and that of isomerisation products of hexene for the dimanganese rhodium catalyst 2 . Par example, 1 generated n‐heptanal/2‐methylhexanal in TOF values of 246 [h^–1] (n/iso = 3.4) and the c,t‐hexenes in that of 241 [h^–1]. Opposotite to this, 2 achieved such values of 55 [h^–1] (n/iso = 3.6) and 473 [h^–1]. A triphenylphosphane substitution product of 1 increased the activity of the hydroformylation reaction about 20%, accompanied by an only gradually improved selectivity. The hydrogenation products like alcohols and saturated hydrocarbons known from industrial hydroformylation processes were not observed. The metals manganese and rhenium bound at the rhodium reaction center showed a cooperative effect.     

Synthese und Struktur chiraler Heterometallatetrahedrane des Typs [Re2(M1PPh3)(M2PPh3)(μ‐PCy2)(CO)7C≡CPh] (M1 = Ag,Au; M2 = Cu,Ag, Au)

Syntheses and Structure of Chiral Metallatetrahedron Complexes of the Type [Re₂(M¹PPh₃)(M²PPh₃)(μ‐PCy₂)(CO)₇C≡CPh] (M¹ = Ag, Au; M² = Cu, Ag, Au) From the reaction of Li[Re₂(μ‐H)(μ‐PCy₂)(CO)₇(C(Ph)O)] ( 1 ) with Ph₃AuC≡CPh both benzaldehyde and the trinuclear complex Li[Re₂(AuPPh₃)(μ‐PCy₂)(CO)₇C≡CPh] ( 2a ) were obtained in high yield. The complex anion was isolated as its PPh₄‐salt 2b . The latter reacts with coinage metal complexes PPh₃M²Cl [M² = Cu, Ag, Au] to give chiral heterometallatetrahedranes of the general formula [Re₂(AuPPh₃)(M²PPh₃)(μ‐PCy₂)(CO)₇C≡CPh] (M² = Cu 3a , Ag 3b , Au 3c ). The corresponding complex [Re₂(AgPPh₃)₂(μ‐PCy₂)(CO)₇C≡CPh] ( 3d ) is obtained from the reaction of [Re₂(AgPPh₃)₂(μ‐PCy₂)(CO)₇Cl] ( 4 ) with LiC≡CPh. 3d undergoes a metathesis reaction in the presence of PPh₃CuCl giving [Re₂(AgPPh₃)(CuPPh₃)(μ‐PCy₂)(CO)₇C≡CPh] ( 3e ) and PPh₃AgCl. Analogous metathesis reactions are observed when 3c is reacted with PPh₃AgCl or PPh₃CuCl giving 3a or 3b , respectively. The reaction of 1 with PPh₃AuCl gives benzaldehyde and Li[Re₂(AuPPh₃)(μ‐PCy₂)(CO)₇Cl] ( 5a ) which upon reaction with PhLi forms the trinuclear complex Li[Re₂(AuPPh₃)(μ‐PCy₂)(CO)₇Ph] ( 6a ). Again this complex was isolated as its PPh₄‐salt 6b . In contrast to 2b , 6b reacts with one equivalent of Ph₃PAuCl by transmetalation to give Ph₃PAuPh and PPh₄[Re₂(AuPPh₃)(μ‐PCy₂)(CO)₇Cl] ( 5b ). The X‐ray structures of the compounds 3a , 3b , 3e and 4 are reported.     

(PPh4)2[Cl2Re(N3S2)(μ‐NSN)(μ‐N≡ReCl3)]2 – ein Rhenium(VII)‐Komplex mit einer Nitrido‐, einer Dinitridosulfato(II)‐ und einer Rhena‐3,5‐dithia‐2,4,6‐triazino‐Funktion

(PPh₄)₂[Cl₂Re(N₃S₂)(μ‐NSN)(μ‐N≡ReCl₃)]₂ – a Rhenium(VII) Complex with a Nitrido, a Dinitridosulfato(II), and a Rhena‐3,5‐dithia‐2,4,6‐triazino Function The title compound has been prepared from PPh₄[Re^VIICl₄(NSCl)₂] with N(SiMe₃)₃ in dichloromethane solution to give red‐brown single crystals, which were suitable for a crystal structure determination. As a by‐product PPh₄[ReNCl₄] is formed. (PPh₄)₂[Cl₂Re^VII(N₃S₂)(μ‐NSN)(μ‐N≡Re^VIICl₃)]₂ ( 1 ): Space group P2₁/c, Z = 2, lattice dimensions at –80 °C: a = 1280.8(2), b = 1017.5(1), c = 2467.8(3) pm, β = 95.04(1)°, R = 0.049. The complex anion of 1 consists of a planar ReN₃S₂‐heterocycle which is connected with the second rhenium atom by a μ‐nitrido bridge as well as by a μ‐dinitridosulfato(II) ligand to form a planar Re₂(N)(NSN) six‐membered heterocycle. This [Cl₂Re(N₃S₂)(μ‐NSN)(μ‐N≡ReCl₃)]^– unit dimerizes via one of the N‐atoms of the (NSN)^4– ligand to give a centrosymmetric Re₂N₂ four‐membered ring.     

Tetra(3‐methoxypropionato)diruthenium(II,III) Units: Supramolecular Organization in the Complex [Ru2(μ‐O2CCH2CH2OMe)4(H2O)2]BF4

The synthesis and characterization of Ru₂Cl(μ‐O₂CCH₂CH₂OMe)₄ ( 1 ), [Ru₂(μ‐O₂CCH₂CH₂OMe)₄(H₂O)₂]BF₄ ( 2 ), PPh₄[Ru₂Cl₂(μ‐O₂CCH₂CH₂OMe)₄] ( 3 ), (PPh₄)₂[Ru₂Br₂(μ‐O₂CCH₂CH₂OMe)₄]NO₃ ( 4 ), and (PPh₄)₂[Ru₂I₂(μ‐O₂CCH₂CH₂OMe)₄]I_0.5(NO₃)_0.5 ( 5 ), are described. The structure of complexes 2 – 5 was established by single crystal X‐ray diffraction. All complexes show a diruthenium(II, III) unit bridged by four 3‐methoxypropionate ligands. The cationic complex 2 have two axially coordinated water molecules, with a Ru–Ru bond distance of 2.2681(12) Å. This complex shows a supramolecular two‐dimensional organization across hydrogen bonded between the axial water molecules and two methoxy groups of adjacent diruthenium units. The metal‐metal bond lengths, in the anionic complexes 3 , 4 , and 5 , are 2.3039(5), 2.3077(6), and 2.3115(8) Å, respectively. These distances are longer than the observed in compound 2 . In the anionic complexes, the axial positions of the diruthenium units are occupied by two halide ligands. Complexes 3 – 5 have PPh₄⁺ cations as counterion, although 4 and 5 are double salts with PPh₄NO₃ and PPh₄I_0.5(NO₃)_0.5, respectively. All compounds have been also characterized by elemental analysis, magnetic measurements, and spectroscopic techniques.     

Umsetzungen von Cp*NbCl4 und Cp*TaCl4 mit Trimethylsilyl‐azid,Me3Si‐N3. Molekülstrukturen der bis(azido)‐oxo‐verbrückten Komplexe [Cp*NbCl(N3)(μ‐N3)]2(μ‐O) und [Cp*TaCl2(μ‐N3)]2(μ‐O) (Cp* = Pentamethylcyclopentadienyl)

Reactions of Cp*NbCl₄ and Cp*TaCl₄ with Trimethylsilyl‐azide, Me₃Si‐N₃. Molecular Structures of the Bis(azido)‐Oxo‐Bridged Complexes [Cp*NbCl(N₃)(μ‐N₃)]₂(μ‐O) and [Cp*TaCl₂(μ‐N₃)]₂(μ‐O) (Cp* = Pentamethylcyclopentadienyl) The chloro ligands in Cp*TaCl₄ (1c) can be stepwise substituted for azido ligands by reactions with trimethylsilyl azide, Me₃Si‐N₃ (A) , to generate the complete series of the bis(azido)‐bridged dimers [Cp*TaCl_3‐n(N₃)_n(μ‐N₃)]₂ ( n = 0 (2c) , n = 1 (3c) , n = 2 (4c) and n = 3 (5c) ). If the solvent CH₂Cl₂ contains traces of water, an additional oxo bridge is incorporated to give [Cp*‐TaCl₂(μ‐N₃)]₂(μ‐O) (6c) or [Cp*TaCl(N₃)(μ‐N₃)]₂(μ‐O) (7c) , respectively. Both 6c and 7c are also formed in stoichiometric reactions from [Cp*TaCl₂(μ‐OH)]₂(μ‐O) (8c) and A . Analogous reactions of Cp*NbCl₄ (1b) with A were used to prepare the azide‐rich dinuclear products [Cp*NbCl_3‐n(N₃)_n(μ‐N₃)]₂ (n = 2 (4b) , and n = 3 (5b) ), and [Cp*NbCl(N₃)(μ‐N₃)]₂(μ‐O) (7b) . The mononuclear complex Cp*Ta(N₃)Me₃ (10c) is obtained from Cp*Ta(Cl)Me₃ and A . All azido complexes were characterised by their IR as well as their ¹H and ¹³C NMR spectra; X‐ray crystal structure analyses are available for 6c and 7b .