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.     

[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 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.     

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.     

Preparation,Crystal Structure and Spectroscopic Studies of Mixed valence Compound [(Cp4i Rh)2 (μ‐Cl)3] [Rh(CO)2Cl2]

[(Cp⁴ⁱ Rh)₂(μ‐Cl)₃] [Rh(CO)₂Cl₂] (Cp⁴ⁱ = tetraisopropyl‐cyclopenta‐dienyl) has been prepared and its crystal is in the space group of Pbar with a= 0.9417 (8), b = 1.4806 (3), c = 1.5062 (2) nm, a = 92.980(10), β = 97.42(3), γ = 93.98 (3)°, V = 2.0735(18) nm³ and Z = 2. The crystal structure consists of a cation of [(η⁵‐Cp⁴ⁱ) Rh (III)(μ‐Cl)₃ Rh (III) (η⁵‐Cp⁴ⁱ)]⁺ and an anion of [Rh (I) (CO)₂ Cl₂]. The two bulky tetraisopropylcyclopentadienyl ligands are in the ecliptic conformation with angle of 10.19° between two cyclopentadienyl ring planes.     

Die Reaktion von tBu2P‐P=P(Me)tBu2 mit [Fe2(CO)9] und [(η2‐C8H14)2Fe(CO)3]

^tBu₂P‐P=P(Me)^tBu₂ reacts with [Fe₂(CO)₉] to give [μ‐(1, 2, 3:4‐η‐^tBu₂P¹‐P²‐P³‐P^4tBu₂){Fe(CO)₃}{Fe(CO)₄}] ( 1 ) and [trans‐(^tBu₂MeP)₂Fe(CO)₃]( 2 ). With [(η²‐C₈H₁₄)₂Fe(CO)₃] in addition to [μ‐(1, 2, 3:4‐η‐^tBu₂P¹‐P²‐P³‐P^4tBu₂){Fe(CO)₂PMe^tBu₂}‐{Fe(CO)₄}] ( 10 ) and 2 also [(μ‐P^tBu₂){μ‐P‐Fe(CO)₃‐PMe^tBu₂}‐{Fe(CO)₃}₂(Fe‐Fe)]( 9 ) is formed. 1 crystallizes in the monoclinic space group P2₁/c with a = 875.0(2), b = 1073.2(2), c = 3162.6(6) pm and β = 94.64(3)?. 2 crystallizes in the monoclinic space group P2₁/c with a = 1643.4(7), b = 1240.29(6), c = 2667.0(5) pm and β = 97.42(2)?. 9 crystallizes in the monoclinic space group P2₁/n with a = 1407.5(5), b = 1649.7(5), c = 1557.9(16) pm and β = 112.87(2)?.     

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.     

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.     

Regioselektive Ringöffnungen von einfach ungesättigten triangularen Clusterkomplexen [M2Rh(μ‐PR2)(μ‐CO)2(CO)8] (M2 = Re2, Mn2; R = Cy,Ph; M2 = MnRe,R = Ph) mit Diphosphanen

Regioselective Ring Opening Reactions of Unifold Unsaturated Triangular Cluster Complexes [M₂Rh(μ‐PR₂)(μ‐CO)₂(CO)₈] (M₂ = Re₂, Mn₂; R = Cy, Ph; M₂ = MnRe, R = Ph) with Diphosphanes Equimolar amounts of the triangular title compounds and chelates of the type (Ph₂P)₂Z (Z = CH₂, DPPM ; C=CH₂, EPP ) react in thf solution at –40 to –20 °C under release of the labile terminal carbonyl ligand attached to the rhodium atom in good yields (70–90%) to ring‐opened unifold unsaturated complexes [MRh(μ‐PR₂)(CO)₄M(DPPM bzw. EPP)(μ‐CO)₂(CO)₃] (DPPM: M₂ = Re₂, R = Cy 1 , Ph 2 ; Mn₂, Cy 5 , Ph 6 ; MnRe, Cy 7 . EPP: M₂ = Re₂, R = Cy 8 ; Mn₂, Cy 10 ). Complexes 1 , 2 and 8 react subsequently under minor uptake of carbon monoxide and formation of the valence saturated complexes [ReRh(μ‐PR₂)(CO)₄M(DPPM bzw. EPP) (CO)₆] (DPPM: R = Cy 3 , Ph 4 . EPP: R = Cy 9 ). Separate experiments ascertained that the regioselective ring opening at the M–M‐edge of the title compounds is limited to reactions with diphosphanes chelates with only one chain member and that the preparation of the unsaturated complexes demands relatively good donor ability of both P atoms. As examples for both types of compounds the molecular structures of 8 and 3 have been determined from single crystal X‐ray structure analysis. Additionally all new compounds are identified by means of ν(CO)IR, ¹H‐ and ³¹P‐NMR data. This includes complexes with a modified chain member in 1 and 5 which, after deprotonation reaction to carbanionic intermediates, could be trapped with [PPh₃Au]⁺ cations as rac‐[MRh(μ‐PR₂)(CO)₄M((Ph₂P)₂CHAuPPh₃)(μ‐CO)₂(CO)₃] (M₂ = Re 17 , Mn 18 ) and products rac‐[MRh(μ‐PR₂)(CO)₄M((Ph₂P)₂CHCH₂R)(μ‐CO)₂(CO)₃] (M₂ = Re, R = Ph 19 , n‐Bu 21 , Me 23 ; Mn, Ph 20 , n‐Bu 22 , Me 24 ) which result from Michael‐type addition reactions of 8 or 10 with strong nucleophiles LiR.     

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)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.     

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.     

Synthese und Kristallstruktur von [C(NMe2)3]2[(CO)4Fe(μ‐InCl2)2Fe(CO)4]

Synthesis and Crystal Structure of [C(NMe₂)₃]₂[(CO)₄Fe(μ‐InCl₂)₂Fe(CO)₄] Treatment of [C(NMe₂)₃]₂[(CO)₄FeInCl₃] ( 1 ) with hot water produces the dinuclear complex [C(NMe₂)₃]₂[(CO)₄Fe(μ‐InCl₂)₂Fe(CO)₄] ( 2 ) which could be crystallized from dichloromethane/pentane. 2 crystallizes in the monoclinic space group P2₁/n with a = 835.7(1), b = 1187.8(1), c = 1902.7(1) pm, β = 91.877(5)° and Z = 2. The anion contains a four‐membered Fe—In—Fe—In ring with octahedral environment at the iron atom and tetrahedral coordination at the In atom.     

Oxidative Addition vs. Ligand-Exchange: Fe(II)-Mixed-Phenylchalcogenolate Complexes fac-[PPN][Fe(CO)3(TePh)n(SePh)3-N] (n = 1, 2)

Diphenyldichalcogenides (PhE)₂ (E = Te, Se) react with Fe(0)-phenylchalcogenolate [PPN] [PhEFe(CO)₄] to yield the products of oxidative addition, Fe(II)-mixed-phenylchalcogenolate fac- [PPN][Fe(CO)₃(TePh)_n(ScPh)_3-n] (n = 1, 2). Reactions of [PPN][REFe(CO)₄] (E=Se, R=Me; E=S, R=Et) and diphenyldichalcogenides yielded ligand-exchange products [PPN][PhEFe(CO)₄] (E=Te, Se, S). The compounds [Fe(CO)₃(TePh)(ScPh)₂]^? (l) and [Fe(CO)₃(TePh)₂ (2) crystallize in the isomorphous monoclinic space group C_2/e, with a = 32.035(8), b = 11.708(6), c = 28.909(6) Å, Z = 8, R = 0.048, and R_w = 0.044 (1); with a = 32.089(5), b= 11.745(2), c = 28.990(8) Å, Z = 8, R = 0.048, and R_w = 0.048 (2). The complexes 1 and 2 crystallize as discrete cations of PPN⁺ and anions of [Fe(CO)₃(TcPh)_u(ScPh)_3-n] (n=1, 2), and one half solvent molecule THF. The geometry around Fe(II) is a distorted octahedron with three carbonyl groups and three phenylchalcogenolate ligands occupying facial positions.     

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.     

Two Fe3(μ3‐S)2(CO)8 clusters with terminal N‐heterocyclic carbenes

The title compounds with terminal N‐heterocyclic carbenes, namely octacarbonyl(imidazolidinylidene‐κC²)di‐μ₃‐sulfido‐triiron(II)(2 Fe—Fe), [Fe₃(C₃H₆N₂)(μ₃‐S)₂(CO)₈], (I), and octacarbonyl(1‐methylimidazo[1,5‐a]pyridin‐3‐ylidene‐κC³)di‐μ₃‐sulfido‐triiron(II)(2 Fe—Fe), [Fe₃(C₈H₈N₂)(μ₃‐S)₂(CO)₈], (II), have been synthesized. Each compound contains two Fe—Fe bonds and two S atoms above and below a triiron triangle. One of the eight carbonyl ligands deviates significantly from linearity. In (I), dimers generated by an N—H...S hydrogen bond are linked into [001] double chains by a second N—H...S hydrogen bond. These chains are packed by a C—H...O hydrogen bond to yield [101] sheets. In (II), dimers generated by an N—H...S hydrogen bond are linked by C—H...O hydrogen bonds to form [111] double chains.     

Synthesis and coordination chemistry of the PPN ligand 2‐[bis(diisopropylphosphanyl)methyl]‐6‐methylpyridine

The synthesis and crystal structure of the multidentate PPN ligand 2‐[bis(diisopropylphosphanyl)methyl]‐6‐methylpyridine (L ), C₁₉H₃₅NP₂, are described. In the isostructural tetrahedral Fe and Co complexes of type LM Cl₂ (M = Fe, Co), namely {2‐[bis(diisopropylphosphanyl)methyl]‐6‐methylpyridine‐κ²P ,N }dichloridoiron(II), [FeCl₂(C₁₉H₃₅NP₂)], and {2‐[bis(diisopropylphosphanyl)methyl]‐6‐methylpyridine‐κ²P ,N }dichloridocobalt(II), [CoCl₂(C₁₉H₃₅NP₂)], the ligand adopts a bidentate P ,N‐coordination, whereas in the case of the octahedral Mn complex {2‐[bis(diisopropylphosphanyl)methyl]‐6‐methylpyridine‐κ²P ,P ′}bromidotricarbonylmanganese(I), [MnBr(C₁₉H₃₅NP₂)(CO)₃], the ligand coordinates via both P atoms to the metal centre.     

A Convenient Synthesis and Molecular Structure of Ru(CO)3[Ph2PN(i‐Bu)PPh2‐P,P]

Ru(CO)₃ [Ph₂PN (i‐Bu) PPh₂‐P, P] was conveniently obtained by the reaction of Ru(DMSO)₄Cl₂ with Ph₂PN(i‐Bu)‐PPb₂ and CO in the presence of Zn powder under mild conditions. The crystal and molecular structure was determined by X‐ray diffraction. This compound possesses a distorted trigonal bipyramidal configuration.     

Insight into the structures of [M(C5H4I)(CO)3] and [M2(C12H8)(CO)6] (M = Mn and Re) containing strong I...O and π(CO)–π(CO) interactions

The compounds tricarbonyl(η⁵‐1‐iodocyclopentadienyl)manganese(I), [Mn(C₅H₄I)(CO)₃], (I), and tricarbonyl(η⁵‐1‐iodocyclopentadienyl)rhenium(I), [Re(C₅H₄I)(CO)₃], (III), are isostructural and isomorphous. The compounds [μ‐1,2(η⁵)‐acetylenedicyclopentadienyl]bis[tricarbonylmanganese(I)] or bis(cymantrenyl)acetylene, [Mn₂(C₁₂H₈)(CO)₆], (II), and [μ‐1,2(η⁵)‐acetylenedicyclopentadienyl]bis[tricarbonylrhenium(I)], [Re₂(C₁₂H₈)(CO)₆], (IV), are isostructural and isomorphous, and their molecules display inversion symmetry about the mid‐point of the ligand C[triple‐bond]C bond, with the (CO)₃M(C₅H₄) (M = Mn and Re) moieties adopting a transoid conformation. The molecules in all four compounds form zigzag chains due to the formation of strong attractive I...O [in (I) and (III)] or π(CO)–π(CO) [in (I) and (IV)] interactions along the crystallographic b axis. The zigzag chains are bound to each other by weak intermolecular C—H...O hydrogen bonds for (I) and (III), while for (II) and (IV) the chains are bound to each other by a combination of weak C—H...O hydrogen bonds and π(Csp²)–π(Csp²) stacking interactions between pairs of molecules. The π(CO)–π(CO) contacts in (II) and (IV) between carbonyl groups of neighboring molecules, forming pairwise interactions in a sheared antiparallel dimer motif, are encountered in only 35% of all carbonyl interactions for transition metal–carbonyl compounds.     

(Ph4P)2[Be3(μ‐OH)3(H2O)6]Cl5: Kristallstruktur und DFT‐Rechnungen

Bis(tetraphenylphosphonium)‐tris(μ‐hydroxo)hexaaquatriberylliumpentachloride, (Ph₄P)₂[Be₃(μ‐OH)₃(H₂O)₆]Cl₅ ( 1 ), was surprisingly obtained by reaction of (Ph₄P)N₃ · n H₂O with BeCl₂ in dichloromethane suspension and subsequent crystallization from acetonitrile to give single crystals of composition 1· 5.25CH₃CN. According to the crystal structure determination space group P , Z = 2, lattice dimensions at 100 K: a = 1354.8(2), b = 1708.7(2), c = 1753.2(2) pm, α = 114.28(1)°, β = 94.80(1)°, γ = 104.51(1)°, R₁ = 0.0586] the [Be₃(μ‐OH)₃(H₂O)₆]³⁺ cations form six‐mem‐bered Be₃O₃ rings with boat conformation and distorted tetrahedrally coordinated beryllium atoms with the terminally coordinated H₂O molecules. The structure ist characterized by a complicated three dimensional hydrogen‐bridging network including O–H ··· O, O–H ··· Cl, and O–H ··· NCCH₃ contacts. DFT calculations result in nearly planar [Be₃(OH)₃] six‐membered ring conformations.