Zur Reaktivität von alkylthioverbrückten 44‐CVE‐triangularen Platinclustern: Umsetzungen mit bidentaten Phosphanliganden

On the Reactivity of Alkylthio Bridged 44 CVE Triangular Platinum Clusters: Reactions with Bidentate Phosphine Ligands The 44 cve (cluster valence electrons) triangular platinum clusters [{Pt(PR₃)}₃(μ‐SMe)₃]Cl (PR₃ = PPh₃, 2a ; P(4‐FC₆H₄)₃, 2b ; P(n‐Bu)₃, 2c ) were found to react with PPh₂CH₂PPh₂ (dppm) in a degradation reaction yielding dinuclear platinum(I) complexes [{Pt(PR₃)}₂(μ‐SMe)(μ‐dppm)]Cl (PR₃ = PPh₃, 3a ; P(4‐FC₆H₄)₃, 3b ; P(n‐Bu)₃; 3e ) and the platinum(II) complex [Pt(SMe)₂(dppm)] ( 4 ), whereas the addition of PPh₂CH₂CH₂PPh₂ (dppe) to cluster 2a afforded a mixture of degradation products, among others the complexes [Pt(dppe)₂] and [Pt(dppe)₂]Cl₂. On the other hand, the treatment of cluster 2a with PPh₂CH₂CH₂CH₂PPh₂ (dppp) ended up in the formation of the cationic complex [{Pt(dppp)}₂(μ‐SMe)₂]Cl₂ ( 5 ). Furthermore, the terminal PPh₃ ligands in complex 3a proved to be subject to substitution by the stronger donating monodentate phosphine ligands PMePh₂ and PMe₂Ph yielding the analogous complexes [{Pt(PR₃)}₂(μ‐SMe)(μ‐dppm)]Cl (PR₃ = PMePh₂, 3c ; PMe₂Ph, 3d ). NMR investigations on complexes 3 showed an inverse correlation of Tolmans electronic parameter ν with the coupling constants ¹J(Pt,P) and ¹J(Pt,Pt). All compounds were fully characterized by means of NMR and IR spectroscopy. X‐ray diffraction analyses were performed for the complexes [{Pt{P(4‐FC₆H₄)₃}}₂(μ‐SMe)(μ‐dppm)]Cl ( 3b ), [Pt(SMe)₂(dppm)] ( 4 ), and [{Pt(dppp)}₂(μ‐SMe)₂]Cl₂ ( 5 ).     

[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)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.     

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.     

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.     

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)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.     

Synthesis and Structures of d10–d10 M2(μ‐dppm)2 Complexes with Sensitive Metal–Metal Distances in Response to the Binding of Sigma Donors

Diphosphine‐bridged dicopper(I) acetate complexes [Cu₂(μ‐dppm)₂(μ‐OAc)]X ( 2 X; X^? = , ) and [Cu₂(μ‐dppm)₂(μ‐OAc)(MeCN)]X ( 4 X) were prepared and the structures of 2 (PF₆ ) and 4 (PF₆ ) determined by X‐ray crystallography. The ground‐state geometries of [Cu₂(μ‐dppm)₂(μ‐OAc)]⁺ and [Cu₂(μ‐dppm)₂(μ‐OAc)(L)]⁺ (L = py, MeCN, THF, acetone, MeOH) were also obtained using density functional theory (DFT). The increased Cu – Cu distances found experimentally and theoretically by comparing the structures of cation [Cu₂(μ‐dppm)₂(μ‐OAc)]⁺ and its derivatives [Cu₂(μ‐dppm)₂(μ‐OAc)(L)]⁺ reflect the binding of various sigma donors (L). When using [Cu₂(μ‐dppm)₂(μ‐OAc)]⁺ as a structure sensor, the electron‐donating strength of a sigma donor can be quantitatively expressed as a DFT‐calculated Cu – Cu distance with the relative strength in the order py > MeCN > THF > acetone > MeOH, as determined.     

Elektrochemische Synthese von Kupfernitrilkomplexen

Electrochemical Synthesis of Copper Nitrile Complexes Electrochemical syntheses of copper nitrile complexes by anodic dissolution of copper and cathodic reduction of malonodinitrile in a one‐step reaction are reported. In the presence of different donors the following compounds are obtained and characterized analytically: {[Cu₂(μ‐CN) · (CH₃CN)₃]CH(CN)₂}_n ( 1 ), {[Cu₂(μ‐CN)(PPh₃)₄]CH(CN)₂}_n ( 2 ) and [Cu₂(μ‐CN)(phen)₂(PPh₃)₂]CH(CN)₂ ( 3 ). As a result of an X‐ray analysis, 3 proved to be an ionic binuclear complex in which the cyano‐bridged Cu^I atoms have distorted tetrahedral coordination sphere. Both the CN group and the dicyanomethanid anion are disordered about centres of inversion.     

Halide Abstraction from Organic Solvents in Reactions of a Copper(I) Alkoxide: Synthesis and Crystal Structures of [Cu5(dppm)(dppm−)2(OtBu)Cl2] and [Cu3(dppm)3Br2][CuBr2]

The synthesis and structures of the two Cu^I halide complexes [Cu₅(dppm)(dppm^?)₂(O^tBu)Cl₂] and [Cu₃(dppm)₃Br₂][CuBr₂] (dppm = Ph₂PCH₂PPh₂, dppm^? = [Ph₂PCHPPh₂]^?) are reported. The compounds were obtained by treating reaction mixtures of [CuO^tBu] and dppm with dichloromethane or dibromomethane.     

Synthesis and Characterization of an Unexpected Asymmetric Binuclear Copper（Ⅰ） Complex Containing 4-Vinyl-pyridine

The asymmetric binuclear copper(I) complex [Cu₂(dppm)₂(C₇H₇N)(μ‐HCOO)](NO₃) (dppm=Ph₂PCH₂PPh₂, C₇H₇N=4‐vinyl‐pyridine) has been prepared and characterized by physicochemical and spectroscopic methods. The complex is photoluminescent at room temperature. It crystallizes in triclinic system, space group P‐1 with a= 1.2719(3) nm, b=1.8637(4) nm, c=1.1656(2) nm, a=97.16(3)°, β= 104.94(3)″, γ=89.39(3)°, V=2.648.1(9) nm³, D_c= 1.390 g.m^?3, Z=2, μ=0.974 mm^?1, R=0.0483 for 5716 independently observed reflections with I>2δ(I). The structure consists of [Cu₂(dppm)₂(C₇H₇N)(μ‐HCOO)]⁺cations and nitrate anions. The copper atoms show different coordination modes: Cu(1) displays a distorted trigonal and Cu(2) a tetrahedred geometry.     

Synthesis and Structural Characterization of Six Pentanuclear and Tetranuclear Mo/W‐Cu‐S Clusters with Bis(diphenylphosphanyl) Methane

Six heterothiometalic clusters, namely, [WS₄Cu₄(dppm)₄](ClO₄)₂ · 2DMF · MeCN ( 1 ), [MoS₄Cu₄(dppm)₄](NO₃)₂ · MeCN ( 2 ) [MoS₄Cu₃(dppm)₃](ClO₄) · 4H₂O ( 3 ), [WS₄Cu₃(dppm)₃](NO₃) · 4H₂O ( 4 ), [WS₄Cu₃(dppm)₃]SCN · CH₂Cl₂ ( 5 ), and [WS₄Cu₃(dppm)₃]I · CH₂Cl₂ ( 6 ) [dppm = bis (diphenylphosphanyl)methane] were synthesized. Compounds 1 – 4 were obtained by the reactions of (NH₄)₂MS₄ (M = Mo, W) with [Cu₂(μ₂‐dppm)₂(MeCN)₂(ClO₄)₂] {or [Cu(dppm)(NO₃)]₂} in the presence of 1,10‐phen in mixed solvent (CH₃CN/CH₂Cl₂/DMF for 1 and 2 , CH₂Cl₂/CH₃OH/DMF for 3 and 4 . Compounds 5 and 6 were obtained by one‐pot reactions of (NH₄)₂WS₄ with dppm and CuSCN (or CuI) in CH₂Cl₂/CH₃OH. These clusters were characterized by single‐crystal X‐ray diffraction as well as IR, ¹H NMR, and ³¹P NMR spectroscopy. Structure analysis showed that compounds 1 and 2 are “saddle‐shaped” pentanuclear cationic clusters, whereas compounds 3 – 6 are “flywheel‐shaped” tetranuclear cationic clusters. In 1 and 2 , the MS₄^2– unit (M = W, Mo) is coordinated by four copper atoms, which are further bridged by four dppm molecules. In compounds 3 – 6 , the MS₄^2– unit is coordinated by three copper atoms and each copper atom is bridged by three dppm ligands.     

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.     

Heterotrimetallic Coordination Polymers: {CuIILnIIIFeIII} Chains and {NiIILnIIIFeIII} Layers: Synthesis,Crystal Structures,and Magnetic Properties

The use of the [Fe^III(AA)(CN)₄]^? complex anion as metalloligand towards the preformed [Cu^II(valpn)Ln^III]³⁺ or [Ni^II(valpn)Ln^III]³⁺ heterometallic complex cations (AA=2,2′‐bipyridine (bipy) and 1,10‐phenathroline (phen); H₂valpn=1,3‐propanediyl‐bis(2‐iminomethylene‐6‐methoxyphenol)) allowed the preparation of two families of heterotrimetallic complexes: three isostructural 1D coordination polymers of general formula {[Cu^II(valpn)Ln^III(H₂O)₃(μ‐NC)₂Fe^III(phen)(CN)₂ {(μ‐NC)Fe^III(phen)(CN)₃}]NO₃ ? 7 H₂O}_n (Ln=Gd ( 1 ), Tb ( 2 ), and Dy ( 3 )) and the trinuclear complex [Cu^II(valpn)La^III(OH₂)₃(O₂NO)(μ‐NC)Fe^III(phen)(CN)₃] ? NO₃ ? H₂O ? CH₃CN ( 4 ) were obtained with the [Cu^II(valpn)Ln^III]³⁺ assembling unit, whereas three isostructural heterotrimetallic 2D networks, {[Ni^II(valpn)Ln^III(ONO₂)₂(H₂O)(μ‐NC)₃Fe^III(bipy)(CN)] ? 2 H₂O ? 2 CH₃CN}_n (Ln=Gd ( 5 ), Tb ( 6 ), and Dy ( 7 )) resulted with the related [Ni^II(valpn)Ln^III]³⁺ precursor. The crystal structure of compound 4 consists of discrete heterotrimetallic complex cations, [Cu^II(valpn)La^III(OH₂)₃(O₂NO)(μ‐NC)Fe^III(phen)(CN)₃]⁺, nitrate counterions, and non‐coordinate water and acetonitrile molecules. The heteroleptic {Fe^III(bipy)(CN)₄} moiety in 5 – 7 acts as a tris‐monodentate ligand towards three {Ni^II(valpn)Ln^III} binuclear nodes leading to heterotrimetallic 2D networks. The ferromagnetic interaction through the diphenoxo bridge in the Cu^II?Ln^III ( 1 – 3 ) and Ni^II?Ln^III ( 5 – 7 ) units, as well as through the single cyanide bridge between the Fe^III and either Ni^II ( 5 – 7 ) or Cu^II ( 4 ) account for the overall ferromagnetic behavior observed in 1 – 7 . DFT‐type calculations were performed to substantiate the magnetic interactions in 1 , 4 , and 5 . Interestingly, compound 6 exhibits slow relaxation of the magnetization with maxima of the out‐of‐phase ac signals below 4.0 K in the lack of a dc field, the values of the pre‐exponential factor (τ_o) and energy barrier (E_a) through the Arrhenius equation being 2.0×10^?12 s and 29.1 cm^?1, respectively. In the case of 7 , the ferromagnetic interactions through the double phenoxo (Ni^II–Dy^III) and single cyanide (Fe^III–Ni^II) pathways are masked by the depopulation of the Stark levels of the Dy^III ion, this feature most likely accounting for the continuous decrease of χ_M T upon cooling observed for this last compound.     

Synthesis,Spectroscopy, and Structures of Mono‐ and Dinuclear Copper(I) Halide Complexes with 1,3‐Imidazolidine‐2‐thiones

Copper(I) halides with triphenyl phosphine and imidaozlidine‐2‐thiones (L ‐NMe, L ‐NEt, and L ‐NPh) in acetonitrile/methanol (or dichloromethane) yielded copper(I) mixed‐ligand complexes: mononuclear, namely, [CuCl(κ¹‐S‐L ‐NMe)(PPh₃)₂] ( 1 ), [CuBr(κ¹‐S‐L ‐NMe)(PPh₃)₂] ( 2 ), [CuBr(κ¹‐S‐L ‐NEt)(PPh₃)₂] ( 5 ), [CuI(κ¹‐S‐L ‐NEt)(PPh₃)₂] ( 6 ), [CuCl(κ¹‐S‐L ‐NPh)(PPh₃)₂] ( 7 ), and [CuBr(κ¹‐S‐L ‐NPh)(PPh₃)₂] ( 8 ), and dinuclear, [Cu₂(κ¹‐I)₂(μ‐S‐L ‐NMe)₂(PPh₃)₂] ( 3 ) and [Cu₂(μ‐Cl)₂(κ¹‐S‐L ‐NEt)₂(PPh₃)₂] ( 4 ). All complexes were characterized with analytical data, IR and NMR spectroscopy, and X‐ray crystallography. Complexes 2 – 4 , 7 , and 8 each formed crystals in the triclinic system with P$\bar{1}$ space group, whereas complexes 1 , 5 , and 6 crystallized in the monoclinic crystal system with space groups P2₁/c, C2/c, and P2₁/n, respectively. Complex 2 has shown two independent molecules, [(CuBr(κ¹‐S‐L ‐NMe)(PPh₃)₂] and [CuBr(PPh₃)₂] in the unit cell. For X = Cl, the thio‐ligand bonded to metal as terminal in complex 4 , whereas for X = I it is sulfur‐bridged in complex 3 .     

Reactions of Ethyne with Some Ruthenium Cluster Complexes Containing dppm

Reactions of ethyne with [Ru₃(μ‐dppm)(CO)₁₀] have given isomeric complexes [Ru₃(μ₃‐C₆H₆)(CO)₆(dppm)], one of which, 2 , contains the dppm chelating an Ru‐atom, together with a hexatrienetriyl ligand attached to the Ru₃ cluster to form a methylideneruthenacyclohexadiene system. The second isomer 3 contains the dppm bridging an Ru−Ru bond, with the C₆H₆ ligand forming a vinylruthenacyclopentadiene system. Also isolated was the open‐chain Ru₃ complex 4 containing a ruthenacyclopentadiene attached to the central Ru‐atom; the other Ru−Ru vector is bridged by a PPh₂CHPPh₂C₄H₅ ligand, formed by a novel insertion of two ethyne molecules into an Ru−P bond. The reaction of ethyne with [Ru₃(μ‐H)(μ₃‐C₂H₂)(CO)₉] proceeded by attack at the coordinated alkyne and at the cluster to give a cluster‐bonded PPh₂CH₂PPh₂CCH system in 7 . Thermolysis of [Ru₃(μ‐H)(μ₃‐C₂SiMe₃)(μ‐dppm)(CO)₇] ( 8 ; refluxing MeOH) in the presence of KF gave [Ru₆(μ‐CCH₂)₂(μ‐dppm)₂(CO)₁₂] ( 9 ; 80%); similar reactions carried out with [RuClCp(PPh₃)₂] also present gave 9 (67%) together with [Ru₃(μ‐H)(μ₃‐C₂H)(μ‐dppm)(CO)₆(PPh₃)] ( 11 ; 23%). The molecular structures of 2 , 3 , 4 , 7 , 9 , and 11 , some as differently solvated forms, have been determined by single‐crystal X‐ray studies.     

Zur Reaktivität von dinuklearen Platina‐β‐diketonen gegenüber Phosphanen: Diacetylplatin(II)‐Komplexe und mononukleare Platina‐β‐diketone

The Reactivity of Dinuclear Platina‐β‐diketones with Phosphines: Diacetylplatinum(II) Complexes and Mononuclear Platina‐β‐diketones Addition of mono‐ and bidentate phosphines or of AsPh₃ to the platina‐β‐diketone [Pt₂{(COMe)₂H}₂(μ‐Cl)₂] ( 1 ) followed by the addition of NaOMe at ?70 °C resulted in the formation of diacetyl platinum(II) complexes cis‐[Pt(COMe)₂L₂] (L = PPh₃, 2a ; P(4‐FC₆H₄)₃, 2b ; PPh₂(4‐py), 2c ; PMePh₂, 2d ; AsPh₃, 2d ) and [Pt(COMe)₂(L??L)] (L??L = dppe, 3b ; dppp, 3c ), respectively. The analogous reaction with dppm afforded the dinuclear complex cis‐[{Pt(COMe)₂}₂(μ‐dppm)₂] ( 4 ) that reacted in boiling acetone yielding [Pt(COMe)₂(dppm)] ( 3a ). The reactions 1 → 2 / 3 were found to proceed via thermally highly unstable cationic mononuclear platina‐β‐diketone intermediates [Pt{(COMe)₂H}L₂]⁺ and [Pt{(COMe)₂H}(L??L)]⁺, respectively, that could be isolated as chlorides for L??L = dppe ( 5a ) and dppp ( 5b ). The reversibility of the deprotonation of type 5 complexes with NaOMe yielding type 3 complexes was shown by the protonation of the diacetyl complex 3b with HBF₄ yielding the platina‐β‐diketone [Pt{(COMe)₂H}(dppe)](BF₄) ( 5c ). All compounds were fully characterized by means of NMR and IR spectroscopies, and microanalyses. X‐ray diffraction analysis was performed for the complex cis‐[Pt(COMe)₂(PPh₃)₂]·H₂O·CHCl₃ ( 2a ·H₂O·CHCl₃).     

Chalkogenoniobate als Ausgangsverbindungen zur Darstellung neuer heterobimetallischer Niobium‐Münzmetall‐Chalkogenido‐Cluster

Chalcogenoniobates as Reagents for the Synthesis of New Heterobimetallic Niobium Coinage Metal Chalcogenide Clusters In the presence of phosphine chalcogenoniobates such as Li₃[NbS₄] · 4 CH₃CN ( I ), (NEt₄)₄[Nb₆S₁₇] · 3 CH₃CN ( II ) and (NEt₄)₂[NbE′₃(E^tBu)] ( III a : E′ = E = S; III b : E = Se, E′ = S; III c : E = E′ = Se) respectively react with copper and gold salts to give a number of new heterobimetallic niobium copper(gold) chalcogenide clusters. These clusters show metal chalcogenide units already known from the complex chemistry of the tetrachalcogenometalates [ME₄]^n– (M = V, n = 3, E = S; M = Mo, W, n = 2, E = S, Se). The compounds 1 – 8 owe a central tetrahedral [NbE₄] structural unit, which coordinates η² from two to five coinage metal atoms, employing the chalcogenide atoms of the [NbE₄] edges. The compounds 9 – 11 have a [M′₂Nb₂E₄] (M′ = Cu, Au) heterocubane unit in common, involving a metal metal bond between the niobium atoms, while the compounds 12 and 13 show a complete and 14 an incomplete [M′₃NbE₃X] heterocubane structure (X = Cl, Br). 15 consists of a Cu₆Nb₂ cube with the six planes capped by μ₄ bridging selenide ligands forming an octahedra. The compounds 1 – 15 are listed below: (NEt₄) [Cu₂NbSe₂S₂(dppe)₂] · 2 DMF ( 1 ), [Cu₃NbS₄(PPh₃)₄] ( 2 ), [Au₃NbSe₄(PPh₃)₄] · Et₂O ( 3 ), [Cu₄NbS₄Cl(PCy₃)₄] ( 4 ), [Cu₄NbS₄Cl(P^tBu₃)₄] · 0,5 DMF ( 5 ), [Cu₄NbSe₄(NCS)(P^tBu₃)₄] · DMF ( 6 ), [Cu₄NbS₄(NCS)(dppm)₄] · Et₂O ( 7 ), [Cu₅NbSe₄Cl₂‐ (dppm)₄] · 3 DMF ( 8 ), [Cu₂Nb₂S₄Cl₂(PMe₃)₆] · DMF ( 9 ), [Au₂Nb₂Se₄Cl₂(PMe₃)₆] · DMF ( 10 ), (NEt₄)₂[Cu₃Nb₂S₄(NCS)₅(dppm)₂(dmf)] · 4 DMF ( 11 ), [Cu₃NbS₃Br(PPh₃)₃(dmf)₃]Br · [CuBr(PPh₃)₃] · PPh₃ · OPPh₃ · 3 DMF ( 12 ), [Cu₃NbS₃Cl₂(PPh₃)₃(dmf)₂] · 1.5 DMF ( 13 ), (NEt₄)[Cu₃NbSe₃Cl₃(dmf)₃] ( 14 ), [Cu₆Nb₂Se₆O₂(PMe₃)₆] ( 15 ). The structures of these compounds were obtained by X‐ray single crystal structure analysis.     

A Dirhoda‐Heterocyclic Carbene

The linear μ‐carbido complex [Rh₂(μ‐C)Cl₂(dppm)₂] (dppm=bis(diphenylphosphino)methane) reacts with dimethylacetylene dicarboxylate (DMAD) to afford [Rh₂(μ‐C)(μ‐DMAD)Cl₂(dppm)₂], which features a bent RhCRh linkage (124.7°) that might be described as a dirhoda‐heterocyclic carbene, as demonstrated by coordination to further metal centers.     

Structural Studies of Several Ru3 and Ru4 Carbonyl Clusters

The preparation, characterisation and single‐crystal XRD molecular structure determinations of the three Ru₃ carbonyl clusters attached to carbon ligands, Ru₃(μ‐H)₃(μ₃‐CBr)(CO)₉ ( 1 ), Ru₃(μ‐H)(μ‐dppm){μ‐C(OMe)}(CO)₈ ( 2 ) and AuRu₃(μ‐H)₂(μ₃‐C=C=CHPh)(CO)₁₀ ( 3 ) are reported, together with the structures of the tetranuclear hydrido‐carbonyls Ru₄(μ‐H)_4–2x(CO)_11+x(PPh₃) (x = 0 4 , 1 5 ).