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1.
Transformations of polymeric trimethylacetate complexes [M(OH) n (OOCCMe3)2 – n ] m (M = Ni (I) and Co (II)) and clusters Ni9(4-OH)3(3-OH)3(-O,O-OOCCMe3)(-O,O"-OOCCMe3)7(3-O,O,O"-OOCCMe3)3(4-O,O,O",O"-OOCCMe3)(HOOCCMe3)4(III) and Co6(3-OH)2(-OOCCMe3)10(HOOCCMe3)4(VIII), which are formed from Iand IIupon their recrystallization from nonpolar solvents, were studied. It was shown that the action of N-phenyl-o-phenylenediamine (L) on Ior IIIresults, depending on the solvent, in different tetranuclear clusters with the hydroxo bridges. For example, in benzene, the L2Ni4(3-OH)2(HOOCCMe3)4(-OOCCMe3)6complex (IX) is formed; its L molecules are coordinated in a monodentate way, whereas in acetonitrile, they chelate to give the {[o-C6H4(NH2)(NHPh)]2Ni4(3-OH)2(MeCN)2(OOCCMe3)2(-OOCCMe3)4} compound (X). Heating of Xin the presence of atmospheric oxygen yields IX, the mononuclear bissemiquinonediimine [o-C6H4(NH)(NPh)]2Ni complex (XI), and water. It was noted that the use of aniline in these reactions affords, independent of the nature of the solvent, only one (NH2C6H5)2Ni4(3-OH)2(HOOCCMe3)4(-OOCCMe3)6cluster (VI); in acetonitrile, this cluster is formed as the solvate VI· 2HOOCCMe3(VIa). When treated with ethanol, Iand IIIgive the Ni4(EtOH)6(3-OH)2(2-OOCCMe3)4(OOCCMe3)2cluster (V), which is structurally close to the known cobalt-containing analog IV. Thermolysis of IVin decalin at 170° causes its dimerization, giving the octanuclear Co8(4-O)2( n -OOCCMe3)12complex (VII) with the tetradentate oxo bridges.  相似文献   

2.
Tetrametal clusters such as Ru4(CO)13(-PPh2)2 and Ru4(CO)10(-PPh2)4 are 64-electron systems and, with five metal-metal interactions, are formally electron rich. In fact these clusters have unusual rhomboidal (or flat butterfly) structures with three or four elongated Ru-Ru bonds. With molecular orbitals antibonding with respect to metal metal interactions occupied in such clusters, facile two electron oxidation or ligand dissociation processes should occur, giving electron precise molecules. The molecule Ru4(CO)13(-PPh2)2 1a undergoes a remarkable, reversible transformation upon loss of CO affording (-H)Ru4(CO)10(-PPh2)[4-1(P),1(P),1(P),1,2-{C6H4}PPh]3 a cluster which contains a five coordinate phosphido bridge and an orthometallated 2 arene ring. This conversion is reversible under CO. These and other results which will be discussed confirm that M4 clusters with electrons in excess of the expected EAN rule count may exhibit unusual reactivity. The solid-state CP/MAS and static powder31P NMR spectra of some of these clusters exhibit99/101Ru-31P couplings, values of which have been measured for the first time.  相似文献   

3.
The complexes Co3(CO)9( 3-X) (X=S, Se) can be reduced to the corresponding anionic species [Co3(CO)9( 3-X)]–, which react with allyl bromide to give Co3(CO)7(- 3-C3H5)( 3-X) (X=S, Se). These are the first two cobalt complexes containing the bridging - 3-allyl ligand. The structure of the selenium complex was determined by X-ray crystallography. Crystal data for Co3(CO)7(- 3-C3H5)( 3-Se) are as follows: space group P21/c, a=9.051(2) Å, b=8.102(2) Å, c=21.27(4) Å, =93.82(3)°, Z=4, and R=0.0565 for 2491 observed reflections.  相似文献   

4.
Triosmium cluster Os3(-H)(CO)10(--2-CCC Me2OMe) (1) was obtained by treating OS3(-H)(-Cl)(CO)10 with LiCCCMe2OMe. The reaction of cluster1 with HBF4 · Et2O at –60 °C leads to the cationic complex [Os3(-H)(CO)10(-,,2-C=C=C Me2)]+BF4 – (2) with an allenylidene ligand. Thes1H and13C NMR spectra of complex2 reveal the temperature dependence caused by migration of hydrocarbon and carbonyl ligands. Thermodynamic parameters were obtained for be exchange process of the allenylidene ligand.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp, 2990–2992, December, 1996.  相似文献   

5.
The reaction of the dinuclear complex Co2(-OOCCMe3)2(2-OOCCMe3)2bpy2 (1) with the polymer [Co(OH) n (OOCCMe3)2–n ] x afforded the unsymmetrical dinuclear complex bpyCo2(2-O,2-OOCCMe3)(2-O,O"-OOCCMe3)2(2-OOCCMe3) (2). The reaction of 2,2"-dipyridylamine with [Co(OH) n (OOCCMe3)2–n ] x gave rise to the analogous complex [(C5H4N)2NH]Co2(2-O,2-OOCCMe3)(-OOCCMe3)2(2-OOCCMe3) (3). The reaction of complex 1 with Ni4(3-OH)2(-OOCCMe3)4(OOCCMe3)2(MeCN)2[2-o-C6H4(NH2)(NHPh)]2 (4) produced an isostructural heterometallic analog of complex 2 with composition bpyM2(2-O,2-OOCCMe3)(2-O,O"-OOCCMe3)2(2-OOCCMe3) (5) (M = Co, Ni; Co : Ni = 1 : 1) and the dinuclear heterometallic complex bpy(HOOCCMe3)M(-OH2)(-OOCCMe3)2M(OOCCMe3)2[o-C6H4(NH2)(NHPh)] (6) (M = Co, Ni; Co : Ni = 0.15 : 1.85). Compounds 2 and 5 exhibit ferromagnetic spin-spin exchange interactions.  相似文献   

6.
The approach based on isomorphous substitution permitted preparation of (Co, Ni)4(acac)4(3–OMe)4(MeOH)4(I) via interaction of individual M4(acac)4(3–OMe)4(MeOH)4 in toluene/methanol media. The oxidation of I in air in solution in MeOH in the presence of NaOAc and aminoalcohols as catalysts gives Co2Ni2-(acac)4(3–OMe)4(OAc)2(II). The symmetrization reaction between a complex formed by a hard Pearson acid and a soft Pearson base and that formed by a soft acid and a hard base led to CuNi2(OCOC2H5)3(ORN)3-(RNOH)(III) and Ni(Ni0.25Cu0.75)2(3–OH)(2–OAc)(OAc)2(2, 2-ORN)3(2-RNOH)(IV) RN = CH(CH3)-CH2NMe2 via interaction of Ni(ORN)2 with copper propionate and copper acetate hydrate respectively in hydrocarbon media.  相似文献   

7.
Summary The dinuclear complexes {RuCp*(-Cl)}2(-dppm) (1) and {RuCp*(-Cl)}2 (-dppe) (3) are obtained by reacting [RuCp*(3-Cl)]4 withdppm, anddppe, respectively.1 is readily oxidized with AgCF3SO3, instead of chloride abstraction, to afford the dinuclear complex [{RuCp*(-Cl)}2(-dppm)](SO3CF3)2 (2) with two metal centers connected by a single Ru-Ru bond. Under the same conditions,3 decomposes to several intractable materials. Similarly to1, RuCp* (dmpe)Cl reacts with AgCF3SO3 to afford the Ru(III) complex [RuCp*(dmpe)Cl](SO3CF3) (4) without no halide abstraction. The crystal structures of2,3, and4 are presented.
Synthese und Röntgenstrukturanalyse einiger ein- und zweikerniger Rutheniumkomplexe mit Bisphosphinliganden
Zusammenfassung Die Komplexe {RuCp*(-Cl)}2(-dppm) (1) und {RuCp*(-Cl2(-dppe) (3) wurden durch Umsetzung von [RuCp*(3-Cl)]4 mitdppm bzw.dppe dargestellt.1 wird durch AgCF3SO3 zum zweikernigen Komplex [{RuCp*(-Cl)}2(-dppm)](SO3CF3)2 (2) oxidiert, welcher eine Ru-Ru-Metallbindung aufweist. Unter den gleiche Reaktionsbedingungen zersetzt sich3 zu undefinierten Produkten. Analog zu1 reagiert RuCp* (dmpe)Cl mit AgCF3SO3 zum Ru(III)-Komplex [Ru(Cp*)(dmpe)Cl](SO3CF3) (4) wobei es zu keiner Chloridabspaltung kommt. Von2,3, und4 wurden die Kristallstrukturen bestimmt.
  相似文献   

8.
The reactions between Ru5( 5-C2PPh2)(gm-PPh2(CO)13 (1) and cyclopentadienes afforded the hexanuclear clusters Ru6( 6-C)( 3-PPh2)2(CO)10(-C5 R 5) [R 5 = H5 (2), H4Me (3), Me5 (4)] which contain an encapsulated carbide and a face-capping 3-CH group, formed by cleavage of CC and CP bonds of the C2PPh2 moiety in1. In the reaction with cyclopentadiene, the unusual ligand C13H12O, formed by combination of C2, CO and two molecules of C5H6 (or one molecule of dicyclopentadien), was characterized in the complex Ru5( 4-PPh) ( 4-C13H12O)(-PPh2(CO)11(-C5H5) (5). In the reaction with pentamethylcyclopentadiene, the vinylidene complex Ru5( 3-CCHPh)( 4-PPh)( 4-PPh) (-PPh2)(CO)9(-C5Me5) (6) was also formed.  相似文献   

9.
Novel anhydrous trinuclear 3-oxo complexes of Cr(III), Cr3(3-O)(CF3COO)6(CH3COOH)2(CF3COO) (I) and of Cr(III,III,II), Cr3(3-O)(CF3COO)6(CH3COOH)2(THF) (II) (where THF is (CH2)4O) are synthesized by anodic dissolution of metallic chromium in solutions of trifluoroacetic acid in acetonitrile and in tetrahydrofuran and their structures are studied by X-ray diffraction analysis. Complex I forms orthorhombic crystals with space group Pna21, a = 9.778(1) , b = 16.042(2) , c = 22.851(4) , Z = 4, R 1 = 0.0332; complex II crystallizes in monoclinic system: space group P21/c, a = 9.866(1) , b = 17.895(2) , c = 21.167(4) , = 100.75(2)°, Z = 4, R = 0.0422. The average Cr-(3-O) distances in compounds I and II are almost equal (1.943(3) and 1.927(3) ). An average length of the Cr-O bond in octahedral surrounding of metal atoms is different in complexes I and II (1.985(4) and 2.003(3) , respectively), which is specified by different oxidation states of the metal atom. The CrCr distances lie in an interval of 3.366(1)–3.337(1) .__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 4, 2005, pp. 266–272.Original Russian Text Copyright © 2005 by Glazunova, Boltalin, Troyanov.  相似文献   

10.
Reaction of Ru4(CO)13(3-PPh) (1) with the 1,3,5-hexatriyne Me3SiCCCCC CSiMe3 under mild thermal conditions affords initially Ru4(CO)10(-CO)2{4-1,1,2-P(Ph)C(CCSiMe3)C(CCSiMe3) (2), via the facile formation of a P–C bond in a manner similar to that demonstrated previously with alkynes and diynes. The 62-CVE cluster 2 readily decarbonylates to give crystallographically characterised Ru4(CO)10(-CO)(4-PPh){4-1,1,2,2-Me3SiCCC2CCSiMe3} (3). Attempts to further incorporate the pendant alkyne moieties in 3 into the Ru4 coordination environment were partially successful with Ru4(CO)10(4-PPh)(4-1,1,3,3-RC4R') (4, R/R'=SiMe3/CCSiMe3) being formed as a minor product together with the unusual toluene coordinated species Ru4(CO)7(6-C6H5Me)(4-PPh)(4-1,1,3,3-Me3SiC4CCSiMe4) (5). Cluster 3 reacts with an excess of Me3SiCCCCCCSiMe3 to give the open chain cluster Ru4(CO)9(3-PPh){4-2,2,4,4,-C4(CCSiMe3)(SiMe3)C4(CCSiMe3)3} (6).  相似文献   

11.
Addition of aqueous HCl to Ru5( 3-C=CH2)(-SMe)2(-PPh2)2(CO)10 afforded the structurally characterized carbyne complex Ru5( 3-SMe)( 3-CMe)(-Cl)(-SMe)(-PPh2)2(CO)9, formed by addition of H to the vinylidene ligand; a Cl atom bridges an Ru–Ru bond.  相似文献   

12.
Treatment of Ru3(CO)12 with dpphSe2 (dpph = 1,6-bis(diphenylphosphino)hexane) in refluxing toluene in the presence of Me3NO afforded two new compounds, Ru3(CO)7(-CO)(3-Se)(-dpph) (1) and Ru3(CO)7(3-Se)2(-dpph) (2). A similar reaction of Ru3(CO)12 with dpppeSe2 (dpppe = 1,5-bis(diphenylphosphino)pentane) gave exclusively Ru3(CO)7(3-Se)2(-dpppe) (3). Treatment of Ru3(CO)12 with dpphS2 and dpppeS2 at 110°C in the presence of Me3NO afforded Ru3(CO)7(3-S)2(-dpph) (4) and Ru3(CO)7(3-S)2(-dpppe) (5), respectively. Reactions of Fe3(CO)12 with dpphSe2 and dpppeSe2, under identical conditions, afforded Fe3(CO)7(3-Se)2(-dpph) (6) and Fe3(CO)7(3-Se)2(-dpppe) (7), respectively. Compounds 1–7 were characterized spectroscopically and the molecular structures of compounds 1–4 were determined by single crystal X-ray crystallography. The core of 1 contains an equilateral triangle of ruthenium atoms with one capping selenium, one bridging dpph, one doubly bridging carbonyl and seven terminal carbonyl ligands. Complexes 2–4 have a square-pyramidal structure with two metal and two chalcogenide atoms alternating in the basal plane and the third metal atom at the apex of the pyramid, and belong to the family of well-known nido clusters with seven skeletal electron pairs.  相似文献   

13.
The reaction of the dinuclear complex Co2(bpy)2(OOCBut)4 with the tetranuclear complex Ni4(3-OH)2(OOCBut)6(EtOH)6 afforded the trinuclear heterometallic complex M3(bpy)2(3-OH)(-OOCBut)4(OOCBut) (6) (M = Ni, Co; Ni : Co = 1.2 : 1) in which two metal atoms are in an octahedral environment and one metal atom is in a tetrahedral environment. The reaction of 2,2"-bipyridine with Co4(3-OH)2(OOCBut)6(HOEt)6 (reagent ratio was 2 : 1) or the reaction of bpy with Co8(4-O)2( n -OOCBut)12 (reagent ratio was 4 : 1) produced a homometallic analog of 6, viz., the trinuclear cluster Co3(bpy)2(3-OH)(-OOCBut)4(OOCBut) (8). The reaction of 1,10-phenanthroline (phen) with the [Co(OH) n (OOCBut)2–n ] x polymer gave the analogous trinuclear cluster (phen)2Co3(3-OH)(2-OOCBut)4(1-OOCBut). Compounds 6 and 8 exhibit antiferromagnetic spin-spin exchange interactions.  相似文献   

14.
Tetrapalladium clusters containing dppa or dppa and dppm bridging ligands were prepared by condensation of dinuclear units. Reaction of [Pd2Cl2(-dppa)2] with [Cu(PPh3)]PF6 (generated in situ in THF) yielded [Pd4(-Cl)2(-dppa)4] (PF6)2 (4) in a virtually quantitative yield but [Pd4(-Cl)2(-dppm)2(-dppa)2] (PF6)2 (6) was best prepared in CH2Cl2 from [Pd2Cl2(-dppm)2] and [Pd2(MeCN)2(-dppa)2](PF6)2 (2). The structure of 6·2(CH3)2CO·2H2O was determined by X-ray diffraction. It consists of a planar, centrosymmetric 10-membered ring structure. The four bridging diphosphine ligands are of two types: two dppa ligands support the Pd Pd bonds [2.6055(4) Å], whereas the two dppm ligands bridge between two palladium atoms separated by 3.722(4) Å, which are also bridged by a chloride ligand.  相似文献   

15.
Schemes of redox transformations were proposed for osmium carbonylhydride clusters: trinuclear (-H)Os3(-CR = CHR')(CO)1 0 (R = R' = H, Ph; R = H, R' = Ph), (-H)2Os3(3-L)(CO)9 (L = C = CHPh, CHCPh), tetranuclear CpMnOs3 (-CH = CHPh)(-H)(-CO)(CO)1 1, and trinuclear Os3(3-C = CHPh)(CO)9. Two-electron reduction of the trinuclear clusters results in elimination of the unsaturated ligand with preservation of the metal framework.  相似文献   

16.
The thermal reaction of Ru3(CO)10(-Ph2PCH2PPh2) (1) with enyne PhCH=CHCCPh afforded the trinuclear ruthenium clusters Ru3(CO)6{3-P(Ph)CH2PPh2}{3-C(Ph)=CHCC(Ph)(1,2-C6H4)C(=0)} (2), Ru3(-H)(CO)5{3-P(Ph)CH2PPh2}{3-C(Ph)=CHCC(Ph)(1,2-C6H4)C(—0)} (3), and Ru3(CO)6(-CO){3-P(Ph)CH2PPh2}{3-C(C=CPh2)CH=C(H)Ph} (4) and also two isomers of Ru3(CO)5(-CO)(-Ph2PCH2PPh2){3-C4Ph2(CH=CHPh)2} (5a and 5b). Clusters 2, 3, and 4 were characterized by IR spectroscopy, 1H and 31P NMR spectroscopy, and X-ray diffraction analysis. The reaction of complex 1 with enyne FcCH=CHCCFc gave rise to the Ru3(CO)6{3-P(Ph)CH2PPh2}{3-C(Fc)=CHCC(Fc)(1,2-C6H4)C(=0)} (6) and Ru3(-H)(CO)5{3-P(Ph)CH2PPh2}{3-C(Fc)=CHCC(Fc)(1,2-C6H4)C(—0)} (7) clusters. According to the spectral data, the latter compounds are isostructural to complexes 2 and 3, respectively.  相似文献   

17.
The reaction of K[Co(CO)4] and PCl2(TMP) at –5°C leads to the unstable and reactive -phosphinidene complex [Co2(CO)6{-P(TMP)}] (1), while the same reaction carried out at 35°C gives the chlorophosphido and phosphinidene bridged cluster [Co3(CO)7{-P(Cl)TMP}{ 3-P(TMP)}] (2) (TMP=2,2,6,6-tetramethylpiperidyl). Compound 1 reacts with dppm (dppm=bis(diphenyl- phosphino)methane) and [Co2(CO)8] to form the more stable substitution product [Co2(CO)4{-P(TMP)}(-dppm)] (3) and [Co4(CO)7(-CO)3{ 3-P(TMP)}] (4) respectively. The first example of a cationic 3-phosphinidene cluster compound [Co3(CO)9{ 3-P(TMP)}][AlCl4] (5) is obtained from reaction of 3 with AlCl3. The X-ray structures of clusters 2 and 5 are discussed.  相似文献   

18.
The synthesis, structural properties, and fluxional behaviour of platinum-triosmium and platinum-triruthenium clusters derived from Os3Pt(-H)2 (CO)10(PR3) and Ru3Pt(-H)(-CC t Bu)(CO)9 (dppe) and related species are described.  相似文献   

19.
Kinetic equations were formulated, which describe coagulation–fragmentation process in a low concentrated suspension flow at a low shear rate. In such a system dispersed phase divided into fine and coarse fractions as the system is brought to equilibrium. Kinetic equations of two-fraction model were formulated. An approximate solution and, in one particular case, the exact solution of these equations were obtained for the equilibrium state. Detailed analysis of equilibrium particle distribution over the mass m was performed for an exponential coagulation kernel = 0 m and an degenerated disintegration kernel = 12, in which the disintegration frequency is an exponential function of aggregate mass 1 = 0 m + , and the probability of the fragment detachment from an aggregate is independent ofm and decreases exponentially with an increase in mass of a fragment: 2 = 0 –1exp(–/0). The equilibrium distribution was shown to exist only at > 0, and in particular, it is described at = = 1 by the f() = 00 –1exp(–/0) and F(m) = Cx –1(x + 1)2 – 1 e –x functions for the particles of fine and coarse fractions (x = m/m 0, = m 0/0, m 0 and 0 are the characteristic masses of coarse and fine fractions, respectively). The particle distribution for the fine fraction at 1 is well approximated by the Gaussian distribution exp[–(m – m 0)2/(4–1 m 00)].  相似文献   

20.
Diphenylphosphine oxidatively adds to the ReRe bonds of Re2 X 4(-dppm)2 (X=Cl or Br; dppm=Ph2PCH2PPh2) and Re2Cl4(-dpam)2 (dpam=Ph2AsCH2AsPh2) to afford the dirhenium(III) complexes Re2(-X)(-PPh2)HX 3(-LL)2. The dppm complexes have also been prepared from the reactions of Re2(-O2CCH3)X 4(-dppm)2 with Ph2PH, and a similar strategy has been used to prepare Re2(-Cl)(-PPh2)HCl3(-dmpm)2 (dmpm=Me2PCH2PMe2) from Re2(-O2CCH3)Cl4(dmpm)2. Phenylphosphine likewise reacts with Re2 X 4(-dppm)2 to give Re2(-X)(-PHPh)HX 3(-dppm)2. An X-ray crystal structure determination on Re2(-Cl)(-PPh2)HCl3(-dppm)2 confirms its edge-shared bioctahedral structure. This complex crystallizes in the space group (No. 148) witha=21.699(3) Å, =84.50(4)°,V=10084(5) Å3, andZ=6. The structure was refined toR=0.049 (R w 0.069) for 5770 data withI>3.0(I). The Re-Re distance is 2.5918(7) Å. Oxidation of the bromide complex Re2(-Br)(-PPh2)HBr3(-dppm)2 with NOPF6 produces the unusual dirhenium(III, II) cation [Re2(-H)(-Br)[P(O)Ph2]Br2(NO)(-dppm)2]+ which has been structurally characterized as its perrhenate salt, [Re2(-H)(-Br)[P(O)Ph2]Br2(NO)(-dppm)2]ReO4 · 2CH2Cl2. This complex crystallizes in the space group (No. 2) witha=14.187(7) Å,b=16.419(5) Å,c=16.729(5) Å, =98.76(2)°, =110.11(3)°, =104.66(3)°,V=3414(6) Å3,Z=2. The structure was refined toR=0.040 (R w =0.051) for 5736 data withI>3.0(I). The presence of a phosphorus-bound [P(O)Ph2]– ligand, a linear nitrosyl and a bridging hydrido ligand has been confirmed. The Re-Re distance is 2.6273(8) Å.  相似文献   

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