Synthesis of nonanuclear heterometallic carbide clusters. Unexpected formation of the [Ru6(CO)16]2-[Pt2(CO)2(dppm)2]2+ ion pair on the way to [Ru6C(CO)16Pt3(dppm)2

A novel trimetallic cluster [Ru5CRh2Pt2(CO)16(dppm)2] was synthesized via coupling of two neutral clusters-[Ru5C(CO)15] and [Rh2Pt2(CO)6(dppm)2]. The structure of this mixed metal complex was established using X-ray crystallography and 31P NMR spectroscopy. It was found that the reaction between [Ru6C(CO)17] and [Pt2(CO)3(dppm)2] leads to spontaneous electron transfer between these polynuclear complexes and results in the formation of an unusually stable cluster "salt" {[Ru6(CO)16]2-[Pt2(CO)2(dppm)2]2+}, which was characterized by crystallographic and spectroscopic methods. Heating of the Ru6-Pt2 ion pair in an autoclave (145 degrees C, 15 atm N2) results in fusion of the metal frameworks to give a nonanuclear mixed metal [Ru6C(CO)16Pt3(dppm)2] cluster in a good yield. The latter complex was obtained earlier as a minor product of another thermal reaction and now has been additionally characterized by 31P NMR spectroscopy.     

High nuclearity PtRh carbonyl clusters. Synthesis and X-ray characterization of the [Pt2Rh9(CO)22]3− trianion

The new mixed PtRh cluster trianion [Pt₂Rh₉(CO)₂₂]^3? has been isolated as a minor product of the pyrolysis of [PtRh₅(CO)₁₅]^?, and has been characterized by X-ray diffraction. The metal skeleton, which has ideal D_3h symmetry, consists of three face-to-face condensed octahedra, as previously found in the isoelectronic species [Rh₁₁CO)₂₃]^3?, with the Pt atoms on the three-fold axis, in the positions of maximum MM connectivity.     

Thermal decomposition of a series of tetranuclear carbonyl clusters Rh4(CO)12, Rh2Co2(CO)12, RhCo3(CO)12 and Co4(CO)12

Decarbonylation of the unsupported clusters Rh₄(CO)₁₂, Rh₂Co₂(CO)₁₂, RhCo₃(CO)₁₂ and Co₄(CO)₁₂ in a stream of hydrogen has been investigated by temperature programmed decomposition. Kinetic parameters for the thermal decomposition are presented, and the stabilities of the clusters are discussed. The profile for evolution of CO from Rh₄(CO)₁₂ indicates that a stable intermediate is formed. In all four cases methane is formed stepwise until most of the CO groups are evolved.     

Synthesis and structures of new heteronuclear cluster complexes [PPh4][Fe4Rh3Se2(CO)16] and [PPh4]2[Fe3Rh4Te2(CO)15]

The reaction of the K₂[Fe₃Q(CO)₉] clusters (Q = Se or Te) with Rh₂(CO)₄Cl₂ under mild conditions is accompanied by complicated fragmentation of cores of the starting clusters to form large heteronuclear cluster anions. The [PPh₄][Fe₄Rh₃Se₂(CO)₁₆] and [PPh₄]₂[Fe₃Rh₄Te₂(CO)₁₅] compounds were isolated by treatment of the reaction products with tetraphenylphosphonium bromide. The structures of the products were established by X-ray diffraction. In both compounds, the core of the heteronuclear cluster consists of two octahedra fused via a common Rh₃ face. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 775–778, May, 2006.     

Syntheses of the new trinuclear ions [Ru3(CO)11]2− and [Os3(CO)11]2−

Stoichiometric reduction of Os₃CO)₁₂ and Ru₃(CO)₁₂ with K and Ca, respectively; yields the two new cluster dianions [Os₃(CO)₁₁]^2? and [Ru₃(CO)₁₁]^2? which have been isolated and characterized. Temperature-dependent ¹³C NMR spectra for [Os₃(CO)₁₁]^2? and infrared spectra of [Os₃(CO)₁₁]^2? and [Ru₃(CO)₁₁]^2? suggest a similar structure for these dianions in which there is a single edge-bridging carbonyl.     

Tellurium-bridged manganese carbonyl clusters: synthesis and structural transformations of [Te4Mn3(CO10]-, [Te2Mn3(CO)9]2-, [Te2Mn3(CO)9]-, and [Te2Mn4(CO)12]2-

The reactions of appropriate ratios of K2TeO3 and [Mn2(CO)10)] in superheated methanol solutions lead to a series of novel cluster anions [Te4Mn3(CO)10] (1), [Te2Mn3(CO)9]2- (2), [Te2Mn3(CO)9]- (3), and [Te2Mn4(CO)12]2- (4). When cluster 1 is treated with [Mn2(CO)10]/KOH in methanol, paramagnetic cluster 2 is formed in moderate yield. Cluster 2 is oxidized by [Cu(MeCN)4]BF4 to give the closo-cluster [Te2Mn3(CO)9]- (3), while treatment of 2 with [Mn2(CO)10]/KOH affords the closo-cluster 4. IR spectroscopy showed that cluster 1 reacted with [Mn2(CO)10] to give cluster 4 via cluster 2. Clusters 1-4 were structurally characterized by spectroscopic methods or/and X-ray analyses. The core structure of 1 can be described as two [Mn(CO)3] groups doubly bridged by two Te2 fragments in a mu2-eta2 fashion. Both [Mn(CO)3] groups are further coordinated to one [Mn(CO)4] moiety. Cluster 2 is a 49 e- species with a square-pyramidal core geometry. While cluster 3 displays a trigonal-bipyramidal metal core, cluster 4 possesses an octahedral core geometry.     

Synthesis and spectroscopy of cis-configured mononuclear palladium(II) and platinum(II) complexes of chalcogeno o-carboranes and structures of [Pt(SCboPh)2(dppm)], [Pt(SeCboPh)2(dppm)], [Pt(SCboS)(PMe2Ph)2] and [Pt(SCboS)(PMePh2)2]

The reactions of [MCl₂(P^∩P)] and [MCl₂(PR₃)₂)] with 1-mercapto-2-phenyl-o-carborane/NaSeCb^oPh and 1,2-dimercapto-o-carborane yield mononuclear complexes of composition, [M(SCb^oPh)₂(P^∩P)], [M(SeCb^oPh)₂(P^∩P)] (M = Pd or Pt; P^∩P = dppm (bis(diphenylphosphino)methane), dppe (1,2-bis(diphenylphosphino)ethane) or dppp (1,3-bis(diphenylphosphino)propane)) and [M(SCb^oS)(PR₃)₂] (2PR₃ = dppm, dppe, 2PEt₃, 2PMe₂Ph, 2PMePh₂ or 2PPh₃). These complexes have been characterized by elemental analysis and NMR (¹H, ³¹P, ⁷⁷Se and ¹⁹⁵Pt) spectroscopy. The ¹J(Pt–P) values and ¹⁹⁵Pt NMR chemical shifts are influenced by the nature of phosphine as well as thiolate ligand. Molecular structures of [Pt(SCb^oPh)₂(dppm)], [Pt(SeCb^oPh)₂(dppm)], [Pt(SCb^oS)(PMe₂Ph)₂] and [Pt(SCb^oS)(PMePh₂)₂] have been established by single crystal X-ray structural analyses. The platinum atom in all these complexes acquires a distorted square planar configuration defined by two cis-bound phosphine ligands and two chalcogenolate groups. The carborane rings are mutually anti in [Pt(SCb^oPh)₂(dppm)] and [Pt(SeCb^oPh)₂(dppm)].     

Synthesis and spectroscopy of cis-configured mononuclear palladium(II) and platinum(II) complexes of chalcogeno o-carboranes and structures of [Pt(SCboPh)2(dppm)], [Pt(SeCboPh)2(dppm)], [Pt(SCboS)(PMe2Ph)2] and [Pt(SCboS)(PMePh2)2]

The reactions of [MCl₂(P^∩P)] and [MCl₂(PR₃)₂)] with 1-mercapto-2-phenyl-o-carborane/NaSeCb^oPh and 1,2-dimercapto-o-carborane yield mononuclear complexes of composition, [M(SCb^oPh)₂(P^∩P)], [M(SeCb^oPh)₂(P^∩P)] (M = Pd or Pt; P^∩P = dppm (bis(diphenylphosphino)methane), dppe (1,2-bis(diphenylphosphino)ethane) or dppp (1,3-bis(diphenylphosphino)propane)) and [M(SCb^oS)(PR₃)₂] (2PR₃ = dppm, dppe, 2PEt₃, 2PMe₂Ph, 2PMePh₂ or 2PPh₃). These complexes have been characterized by elemental analysis and NMR (¹H, ³¹P, ⁷⁷Se and ¹⁹⁵Pt) spectroscopy. The ¹J(Pt–P) values and ¹⁹⁵Pt NMR chemical shifts are influenced by the nature of phosphine as well as thiolate ligand. Molecular structures of [Pt(SCb^oPh)₂(dppm)], [Pt(SeCb^oPh)₂(dppm)], [Pt(SCb^oS)(PMe₂Ph)₂] and [Pt(SCb^oS)(PMePh₂)₂] have been established by single crystal X-ray structural analyses. The platinum atom in all these complexes acquires a distorted square planar configuration defined by two cis-bound phosphine ligands and two chalcogenolate groups. The carborane rings are mutually anti in [Pt(SCb^oPh)₂(dppm)] and [Pt(SeCb^oPh)₂(dppm)].     

Synthesis,Reactivity, and Fluxional Behaviour of [Ir2Rh2(CO)12], and Crystal Structure of [Ir2Rh2(CO)8(norbornadiene)2]

The synthesis of [Ir₂Rh₂(CO)₁₂] ( 1 ) by the literature method gives a mixture 1 /[IrRh₃(CO)₁₂] which cannot be separated using chromatography. The reaction of [Ir(CO)₄]^? with 1 mol-equiv. of [Rh(CO)₂(THF)₂]⁺ in THF gives pure 1 in 61% yield. Crystals of 1 are highly disordered, unlike those of its derivative [Ir₂Rh₂(CO)₅(μ₂-CO)₃(norbornadiene)₂] which were analysed using X-ray diffraction. The ground-state geometry of 1 in solution has three edge-bridging CO's on the basal IrRh₂ face of the metal tetrahedron. Time averaging of CO's takes place above 230 K. The CO site exchange of lowest activation energy is due to one synchronous change of basal face, as shown by 2D- and VT-¹³C-NMR. Substitution of CO by X^? in 1 takes place at a Rh-atom giving [Ir₂Rh₂(CO)₈(μ₂-CO)₃X]^? (X = Br, I). Substitution by bidentate ligands gives [Ir₂Rh₂(CO)₇(μ₂-CO)₃(η⁴-L)] (L = norbornadiene, cycloocta-1,5-diene) where the ligand L is chelating a Rh-atom of the basal IrRh₂ face. Carbonyl substitution by tridentate ligands gives [Ir₂Rh₂(CO)₆(μ₂-CO)₃(μ₃-L)] (L = 1,3,5-trithiane, tripod) with L capping the triangular basal face of the metal tetrahedron. Carbonyl scrambling is also observed in these substituted derivatives of 1 and is mainly due to the rotation of three terminal CO's about a local C₃ axis on the apical Ir-atom.     

Synthesis and structural characterization of the hydrido carbido ruthenium cluster [PPh4][Ru6C(CO)16H]

According to the protonation of [PPh₄]₂[Ru₆C(CO)₁₆] (1b) withp-toluene-sulfonic acid, a hydrido ruthenium cluster [PPh₄][Ru₆C(CO)₁₆H] (3b) was obtained in 53% yield, which readily decomposed in protic solvents even at –20°C to yield1b, Ru₆C(CO)₁₆H₂, and Ru₅C(CO)₁₅. Cluster3b was characterized by single-crystal X-ray analysis. The six metal atoms are arranged in the form of an octahedron with the carbido ligand located in the center. There are 13 terminal carbonyl, three bridging carbonyl, and a bridging hydrido ligands.     

Reactions of carbonyl clusters with heterobidentate ligands. Synthesis and structural characterization of H4Ru4(CO)10[k2(P,S)-Ph2P(2-CH3SC6H4)] and Rh6(CO)14[k2(P,S)-Ph2P(2-CH3SC6H4)] clusters

Two new disubstituted derivatives of the clusters Rh₆(CO)₁₆ and H₄Ru₄(CO)₁₂ with the heterobidentate ligand [Ph₂P(2-CH₃SC₆H₄)] were synthesized. Structures of these compounds were completely characterized both in solid phase and solution. The H₄Ru₄(CO)₁₀[k²(P,S)-Ph₂P(2-CH₃SC₆H₄)] cluster is an example of a structure, in which a chelating coordination of a heterobidentate ligand results in the occurrence of a center of asymmetry associated with the substituted metal atom. This type of polynuclear complexes is of interest for obtaining essentially new catalysts for asymmetric synthesis on the basis of cluster compounds.     

Syntheses, characterization, and luminescence of Pt II-M I (M = Cu, Ag, Au) heterometallic complexes by incorporating Pt(diimine)(dithiolate) with [M2(dppm)2]2+ (dppm = Bis(diphenylphosphino)methane)

Reaction of Pt(diimine)(edt) (edt = 1,2-ethanedithiolate) with M(2)(dppm)(2)(MeCN)(2)(2+) (dppm = bis(diphenylphosphino)methane) gave heterotrinuclear complexes [PtCu(2)(edt)(mu-SH)(dppm)(3)](ClO(4)) (11) and [PtCu(2)(diimine)(2)(edt)(dppm)(2)](ClO(4))(2) (diimine = 2,2'-bpyridine (bpy), 12; 4,4'-dibutyl-2,2'-bipyridine (dbbpy), 13; phenanthroline (phen), 14; 5-bromophenanthroline (brphen), 15) when M = Cu(I). The reaction, however, afforded tetra- and trinuclear complexes [Pt(2)Ag(2)(edt)(2)(dppm)(2)](SbF(6))(2) (17) and [PtAu(2)(edt)(dppm)(2)](SbF(6))(2) (21) when M = Ag(I) and Au(I), respectively. The complexes were characterized by elemental analyses, electrospray mass spectroscopy, (1)H and (31)P NMR, IR, and UV-vis spectrometry, and X-ray crystallography for 14, 17, and 18. The Pt(II)Cu(I)(2) heterotrinuclear complexes 11-15 exhibit photoluminescence in the solid states at 298 K and in the frozen acetonitrile glasses at 77 K. It is likely that the emission originates from a ligand-to-metal charge transfer (dithiolate-to-Pt) (3)[p(S) --> d(Pt)] transition for 11 and from an admixture of (3)[d(Cu)/p(S)-pi(diimine)] transitions for 12-16. The Pt(II)(2)Ag(I)(2) heterotetranuclear complexes 17 and 18 are nonemissive in the solid states and in solutions at 298 K but show photoluminescence at 77 K. The Pt(II)Au(I)(2) heterotrinuclear complexes 19-21, however, are luminescent at room temperature in the solid state and in solution. Compounds 19 and 20 afford negative solvatochromism associated with a charge transfer from an orbital of a mixed metal/dithiolate character to a diimine pi orbital.     

Mixed Co-Rh nitrido-encapsulated carbonyl clusters. synthesis, solid-state structure, and electrochemical/EPR characterization of the anions [Co10Rh(N)2(CO)21]3-, [Co10Rh2(N)2(CO)24]2-, and [Co11Rh(N)2(CO)24]2-

The nitrido-encapsulated heterometallic cluster anions [Co(10)Rh(N)2(CO)21](3-) (1), [Co(10)Rh2(N)2(CO)24](2-) (2), and [Co(11)Rh(N)2(CO)24](2-) (3) have been obtained by tailored redox-condensation reactions. These three anions are rare high-nuclearity mixed-metal clusters containing two interstitial nitrogen atoms. Their structures have been determined by single-crystal X-ray diffraction on their [NR4]+ salts (R = Me for 1 and 3, R = Et for 2), and their electrochemical and ESR properties have been studied in detail. It is noteworthy that 1 has an unprecedented stereochemistry that does not exhibit a close geometrical resemblance with the isoelectronic homometallic anion [Co(11)N2(CO)11(mu2-CO)10](3-), and 2, despite its even number of electrons, is a paramagnetic species.     

A diplatinum complex containing one bridging and two chelating dppm ligands. The X-ray structure analysis of [Pt2 (dppm)3] [PF6]2 (dppm = Ph2CH2PPh2)

The dinuclear platinum(I) complex [Pt₂(dppm)₃][PF₆]₂ unexpectedly contains a PtPt bond, one bridging and two chelating dppm ligands, in marked contrast to the related zerovalent platinum compound [Pt₂(dppm)₃].     

Reactivity of the heterometallic clusters [HMCo3(CO)12] and [Et4N][MCo3(CO)12] (M = Fe, Ru) toward phosphine selenides, including selenium transfer. Crystal structures of [HRuCo3(CO)7(mu-CO)3(mu-dppy)], [MCo2(mu3-Se)(CO)7(mu-dppy)], and [RuCo2(mu3-Se)(CO)7(mu-dppm)] [dppy = Ph2(2-C5H4N)P, dppm = Ph2PCH2PPh2

The reactivity of [HMCo3(CO)12] and [Et4N][MCo3(CO)12] (M = Fe, Ru) toward phosphine selenides such as Ph3PSe, Ph2P(Se)CH2PPh2, Ph2(2-C5H4N)PSe, Ph2(2-C4H3S)PSe, and Ph2[(2-C5H4N)(2-C4H2S)]PSe has been studied with the aim to obtain new selenido-carbonyl bimetallic clusters. The reactions of the hydrido clusters give two main classes of products: (i) triangular clusters with a mu3-Se capping ligand of the type [MCo2(mu3-Se)(CO)(9-x)L(y)] resulting from the selenium transfer (x = y = 1, 2, with L = monodentate ligand; x = 2, 4, and y = 1, 2, with L = bidentate ligand) (M = Fe, Ru) and (ii) tetranuclear clusters of the type [HMCo3(CO)12xL(y)] obtained by simple substitution of axial, Co-bound carbonyl groups by the deselenized phosphine ligand. The crystal structures of [HRuCo3(CO)7(mu-CO)3(mu-dppy)] (1), [MCo2(mu3-Se)(CO)7(mu-dppy)] (M = Fe (16) or Ru (2)), and [RuCo2(mu3-Se)(CO)7(mu-dppm)] (12) are reported [dppy = Ph2(2-C5H4N)P, dppm = Ph2PCH2PPh2]. Clusters 2, 12, and 16 are the first examples of trinuclear bimetallic selenido clusters substituted by phosphines. Their core consists of metal triangles capped by a mu3-selenium atom with the bidentate ligand bridging two metals in equatorial positions. The core of cluster 1 consists of a RuCo3 tetrahedron, each Co-Co bond being bridged by a carbonyl group and one further bridged by a dppy ligand. The coordination of dppy in a pseudoaxial position causes the migration of the hydride ligand to the Ru(mu-H)Co edge. In contrast to the reactions of the hydrido clusters, those with the anionic clusters [MCo3(CO)12]- do not lead to Se transfer from phosphorus to the cluster but only to CO substitution by the deselenized phosphine.     

Halogenation behaviour of bidentate ligand-bridged derivatives of [Ru3(CO)12] and [Os3(CO)12]

Reaction of the ligand-bridged derivatives [M₃(CO)₁₀{μ-(RO)₂PN(Et)P(OR)₂}] and [M₃(CO)₈{μ-(RO)₂PN(Et)P(OR)₂}₂] (M = Ru or Os; R = Me or Prⁱ) with halogens leads to the formation of cationic products [M₃(μ-X)(CO)₁₀{μ- (RO)₂PN(Et)P(OR)₂}]⁺ and [M₃(μ-X)(CO)₈{μ-(RO)₂PN(Et)P(OR)₂}₂]⁺ (X = Cl, Br or I) in which the halogen bridges an opened edge of the metal atom framework; the crystal structure of [Ru₃(μ-I)(CO)₈{μ-(MeO)₂PN(Et)P(OMe)₂}₂]PF₆ is reported.     

双膦钌配合物Ru（OAc）2（Ph3P）（dppm）和Ru（OAc）2（dppm）2的合成和催化性能

合成了双膦醋酸钌合作物，不同温度的＾１Ｈ ＮＭＲ谱表明，两个醋酸根分别以单齿和双齿配体与中心钌（Ⅱ）配位；＾３１Ｐ ＮＭＲ和Ｘ－射线结构分析表明膦配体为面式构型。配合物对丙烯酸和苯乙烯有选择氢化活性。     

Synthesis and structural characterization of heterometallic thorium aluminum polynuclear molecular clusters

Aluminum can undergo hydrolysis in aqueous solutions leading to the formation of soluble molecular clusters, including polynuclear species that range from 1 to 2 nm in diameter. While the behavior of aluminum has been extensively investigated, much less is known about the hydrolysis of more complex mixed-metal systems. This study focuses on the structural characteristics of heterometallic thorium-aluminum molecular species that may have important implications for the speciation of tetravalent actinides in radioactive waste streams and environmental systems. Two mixed metal (Th(4+)/Al(3+)) polynuclear species have been synthesized under ambient conditions and structurally characterized by single-crystal X-ray diffraction. [Th(2)Al(6)(OH)(14)(H(2)O)(12)(hedta)(2)](NO(3))(6)(H(2)O)(12) (ThAl1) crystallizes in space group P2(1)/c with unit cell parameters of a = 11.198(1) ?, b = 14.210(2) ?, c = 23.115(3) ?, and β = 96.375° and [Th(2)Al(8)(OH)(12)(H(2)O)(10)(hdpta)(4)](H(2)O)(21) (ThAl2) was modeled in P1? with a = 13.136(4) ?, b = 14.481(4) ?, c = 15.819(4) ?, α = 78.480(9)°, β = 65.666(8)°, γ = 78.272(8)°. Infrared spectra were collected on both compounds, confirming complexation of the ligand to the metal center, and thermogravimetric analysis indicated that the thermal degradation of these compounds resulted in the formation of an amorphous product at high temperatures. These mixed metal species have topological relationships to previously characterized aluminum-based polynuclear species and may provide insights into the adsorption of tetravalent actinides on colloidal or mineral surfaces.