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1.
The clusters Fe2Ru(CO)12–n
(CNBu
t
)
n
(3, n=1; 4, n=2), FeRu2(CO)12–n
(CNBu
t
)
n
(5, n=1, 6, n=2) and FeRu2(CO)11(CNCy) (5a) have been prepared by direct substitution from the parent carbonyl precursors Fe2Ru(CO)12 (1) and FeRu2(CO)12 (2). All compounds have been characterized spectroscopically and clusters 3, 4, 5, and 6 by single crystal X-ray determinations. In all cases, the isonitrile ligands adopt axial or pseudo-axial positions on a ruthenium atom. The structures of 3–5 are very similar to their parent clusters, but the extent of metal framework disorder is significantly less. Cluster 6 adopts the same C
2v Fe3(CO)12 type structure as 4, and thus differs markedly from the parent compound 2, which has a D
3 structure . 相似文献
2.
Eliano Diana Giuliana Gervasio Domenica Marabello Rosanna Rossetti 《Journal of Cluster Science》1998,9(3):223-242
Co2(CO)8 and Te2O react to form the well known Co4(CO)10Te2, Co4(CO)11Te2 complexes and the two new cluster complexes CCo6(CO)12Te2(1), and CCo6(CO)10Te2(Te3) (2). The structures of 1 and 2 were determined by X-ray analysis, together with the triphenylphosphine derivative of 1, CCo6(CO)11(PPh3)Te2(3), which was analyzed to clarify the disordered structure of the parent compound. Complex 1 is formed by a prismatic cluster of cobalt atoms with a carbon embedded in the cage; two tellurium atoms cap the triangular faces of the prism and each cobalt atom links two terminal carbonyl groups. The complex 2 has a similar prismatic cage CCo6; two 4-Te atoms cap two rectangular faces of the prism, while other two Te atoms bridge two edges of the triangular faces and are linked each other through a third Te atom. Electron counting gives for complex 2 92 electrons: the presence of two long Co–Co distances suggests that the two excess electrons are located on Co–Co antibonding orbitals. Crystal data for 1, space group C2/c, a = 12.845(2) Å, b = 13.449(2) Å, c = 13.246(2) Å, = 91.95(2)°, Z = 4, R = 0.097 for 2555 reflections; for 2, space group Pnna, a = 17.219(5) Å, b= 14.969(6) Å, c = 9.178(4) Å, Z = 4,R = 0.037 for 3103 reflections; for 3, space group P21/c, a = 9.288(2) Å, b = 14.920(6) Å, c = 26.300(9) Å, = 99.99(2)°, Z = 4, R = 0.037 for 4300 reflections. The vibrational analysis of the complex 1 was performed and most of the (CO), (6C–Co), (Co–Co) and (Co–Co) modes were assigned. The (Co–Te) modes were interpreted on the basis of the intermolecular coupling, due to the close contact between neighboring clusters in one distinct direction in the crystal. 相似文献
3.
S. P. Tunik S. I. Pomogailo G. I. Dzhardimalieva A. D. Pomogailo I. I. Chuev S. M. Aldoshin A. B. Nikol'skii 《Russian Chemical Bulletin》1993,42(5):937-942
Mono- and disubstituted cluster metal-containing monomers were obtained under mild conditions on interaction of Rh6(CO)16 with 4-vinylpyridine (4-ViPy) in the presence of N-trimethylaminoxide. These products were characterized by IR and1H NMR spectroscopy and by elemental and X-ray analyses. Rh6(CO)15(4-ViPy) was found to be an octahedral cluster with eleven terminal and four 3-bridging carbonyl ligands. 4-ViPy is linked with the Rh(3) atom through the N atom and occupies the coordination site of the twelfth CO terminal ligand. The mean value of the Rh-Rh bond length is 2.762 Å. The unsaturated ligand has little or no effect on the geometry of the starting cluster and its double bond retains the ability to undergo addition reactions.For part 28, seeRuss. Chem. Bull., 1993, 453.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 975–979, May, 1993. 相似文献
4.
Iwao Ojima Robert J. Donovan Patrizia Ingallina Núria Clos William R. Shay Masakatsu Eguchi Qingping Zeng Anna Korda 《Journal of Cluster Science》1992,3(4):423-438
The reactions of hydrosilane and/or alkyne as well as isonitriles with rhodium and rhodium cobalt mixed metal carbonyl clusters, e.g., Rh4(CO)12 and Co2Rh2(CO)12, are studied. Novel mixed metal complexes, e.g., CoRh(CO)5 (HCCBu
n
), (R3Si)2Rh(CO)
n
Co(CO)4, Rh(R–NC)4Co(CO)4, Co2Rh2(CO)10(HCCR), and Co2Rh2(CO)9(HCCBu
n
), are synthesized and identified. The catalytic activities of these rhodium and rhodium-cobalt mixed metal complexes are examined in hydrosilyation, silylformylation, and novel silylcarbocyclization reactions. Possible mechanisms for these reactions are proposed and discussed. 相似文献
5.
The interaction of iron carbonyls Fe
n
(CO)
m
(wheren = 1,m = 5;n = 2,m = 9;n = 3,m = 12) with anionic Lewis bases (H–, F–, Cl–, Br– , I–, CN–, SCN–, N3
–, MeSO3
–, MeCO2
–, CF3CO2
–, S2
–, CO3
2–, and SO4
2–) passes through two-stage redox-disproportionation. The first stage is the formation of an iron carbonyl-base complex, [Fe
n
(CO)
m–1C(O)L]–, and the second is a single-electron reduction of this complex by another molecule of the initial iron carbonyl, giving rise to Fe(l) and Fe(–l) derivatives.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 248–249, January, 1996. 相似文献
6.
A. S. Batsanov O. S. Manole Yu. T. Struchkov G. P. Zol'nikova D. N. Kravtsov 《Russian Chemical Bulletin》1993,42(2):359-364
Complexes of Fe(II) and Ru(II) of the general formula Cp(OC)2MOC(O)C6H4X-p, where M=Fe, X=H, F (1, 2) or M=Ru, X=H, F (3, 4) have been prepared by reactingp-XC6H4COOAg with [CpFe(CO)2]2 or CpRu(CO)2I. The crystal structures of complexes1–3 have been determined using X-ray diffraction. Compounds1 and3 are isomorphous. The COO group in1–3 is coordinated as a monodentate ligand. As the latter and the CO ligands are electronically non-equivalent, the coordination of the Cp ligand to the metal is slightly asymmetric.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 395–399, February, 1993. 相似文献
7.
V. I. Koval'chuk B. N. Kuznetsov N. M. Mikova A. A. Efremov N. I. Bakhmutova 《Russian Chemical Bulletin》1993,42(6):1032-1038
Bimetallic catalysts (Fe+Co)/SiO2 were prepared by impregnation of SiO2 with solutions of carbonyl clusters [FeCo3(CO)12][(C2H5)4N], [Fe3Co(CO)13][(C2H5)4N], HFeCo3(CO)12, [Fe5CoC(CO)16][(C2H5)4N], and Co2(CO)8, Fe(CO)5. At 20 °C, no reaction occurs between the compounds supported and the surface of the support. The stability of the supported clusters to thermodecarboxylation in a hydrogen atmosphere depends on their composition and is the highest for the catalyst [FeCo3(CO)12]–/SiO2. The catalytic properties of supported clusters in CO hydrogenation are mostly determined by the preactivation technique. The properties of Fe-Co catalysts which were pretreated at high temperatures, are in general similar to those of standard metal catalysts. Product distribution for the same samples prepared without preactivation does not fit the Schulz-Flory equation. The catalyst HFeCo3(CO)12/SiO2 favors the formation ofC
1–C11 hydrocarbons in the temperature range of 468–473 K; the catalyst [Fe3Co(CO)13]–/SiO2 gives ethylene in the temperature range of 453–473 K.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1079–1085, June, 1993. 相似文献
8.
《Journal of Coordination Chemistry》2012,65(1-4):141-149
Abstract Reactions of metal carbonyl cations (M(CO)6 +, M = Mn, Re) with hydride-, methide- or halide-containing metal carbonyl anions (Fe(CO)4R?, R = H, Me; W(CO)5R?, R = H, Me, Cl, Br, I) produce products that indicate several mechanisms are operative. Reactions of the halo-tungsten complexes produce neutral, solvated tungsten complexes, W(CO)5(CH3CN) and W(CO)4(CH3CN)2 and M(CO)5X in a reaction that appears to be initiated by decomposition of W(CO)5X?. In contrast, the tungsten hydride and methide complexes react, predominantly, by transfer of the hydride or methide to a carbonyl of the cation at a much faster rate. The iron hydride and methide complexes react by iron-based nucleophilicity involving a two-electron process. 相似文献
9.
[Pt12(CO)24]2–/NaY and [Pt9(CO)18]2–/NaY exhibited much higher activities in the CO+NO reaction at 473 K compared with Pt/Al2O3. Kinetic study andin-situ FTIR results suggest that NO adsorption is the rate-limiting step in the CO+NO reaction on intrazeolite Pt carbonyl clusters. 相似文献
10.
η2-Acyl and σ-Alkyl(carbonyl) Coordination in Molybdenum and Tungsten Complexes: Synthesis and Studies of the Isomerization Equilibria and Kinetics The anionic molybdenum and tungsten complexes [LRM(CO)3]? (LR? = [(C5H5)Co{P(O)R2}3]?, R = OCH3, OC2H5, O-i-C3H7; M = Mo, W) have been alkylated with the iodides R′ I, R′ = CH3, C2H5, i-C3H7, and CH2C6H5. The reactivity pattern of the alkylation is in accord with a SN2 mechanism. Depending on M, R′, reaction temperature, and time the η-alkyl (carbonyl) compounds [LRM(CO)3R′] and/or the isomeric η2-acyl compounds [LRM(CO)2(η2-COR′)] can be obtained. 8 new σ-alkyl(carbonyl) compounds and 15 new η2-acyl compounds have been isolated and characterized. The 1H NMR and the IR spectra give conclusive evidence that the σ-alkyl(carbonyl) compounds [LRM(CO)3R′] are formed as the primary products of the alkylation and that they isomerize partly or completely to give the η2-acyl compounds [LRM(CO)2(η2-COR′)]. The position of the equilibrium σ-alkyl(carbonyl)/η2-acyl is controlled by the steric demands of the groups R′ and the ligands LR?. The molybdenum compounds isomerize much more readily than the tungsten compounds. The rate constants of the isomerization processes [LRMo(CO)3CH3] → [LRMo(CO)2(η2-COCH3)], R = OCH3, OC2H5, and O-i-C3H7, measured at 305 K in acetone-d6, are 6–8 x 10?3 s?1. 相似文献
11.
Summary Rhodium(I) carbonyl complexes, namely Rh(CO)X(R2SO)2 (R = Me, n-Pr or n-Bu) and Rh(CO)X(R2S)2 (R = Me, Et or i-Pr) and X = CI or Br, have been prepared and characterized. The compounds Rh(CO)X[P(OPh)3]2 X = Cl or Br, have also been isolated. In the R2SO and R2S complexes, the carbonyl stretching frequencies occur atca. 2020–2025 cm–1 andca. 1950–1980 cm–1 respectively. In the R2SO ligand containing complexes v(S-O) occurs atca. 1100–1125 cm–1 indicative of metal-sulphur coordination. In presence of HBF4, the addition of an excess of Me2SO to (OC)2Rh(-Cl)2Rh(CO)2 gives [Rh(Me2SO)6]3+ in which the central metal atom undergoes spontaneous oxidation from Rh1(d8) to RhIII(d6). The complexes have been characterized additionally by u.v.vis. spectra, conductivity measurements and by elemental analyses. 相似文献
12.
Angelo J. Amoroso Brian F. G. Johnson Jack Lewis Chi-Keung Li Catherine A. Morewood Paul R. Raithby Maria D. Vargas Wing-Tak Wong 《Journal of Cluster Science》1995,6(1):163-173
Reduction of the heptaosmium cluster [Os7(CO)21] With [Et4N][NH4) gives the cluster dianion [Os7(CO)20]2–,1, in high yield. The reaction of the dianion with [AuPR
3Cl] (R=Et or Ph) in the presence of TlPF6 forms [Os7((CO)20(AuPR
3)2] [R=Et (2a);R = Ph(2b)] in 80% yield, while the corresponding reaction with (Os(C6H6)(CH3CN)3]2+ gives [Os8(CO)20 (
6-C6H6)] (3) in reasonable yield (ca. 30%). The dianion,1, and the clusters2 and3 have been fully characterized by bout spectroscopic and crystallographic methods. The crystal structure of the [Ph4P]+ salt of1 shows that the metals in the anion adopt a capped octahedral geometry, with all twenty carbonyl ligands in terminal sites. The metal core geometry in2a is best described as a tricapped octahedron, and is based on the structure of the dianion1 with two adjacent octahedral faces capped by the Au atoms of the two AuPEt3 groups. In a similar fashion, the geometry of3 is related to that of1 with the addition of an Os(C6H6) unit capped to a triangular face, to give a bicapped octahedral framework. 相似文献
13.
Giuliana Gervasio Fabrizio Musso Sándor Vastag György Bor Gábor Szalontai László Markó 《Journal of Cluster Science》1994,5(3):401-417
Co2(CO)8 and Me2P(S)P(S)Me2 react to form the two cluster complexes: Co4(CO)9S(PMe2)2) (1) and Co3(CO)7S(SPMe2) (2). The strucure of1 and of the disubstituted triphenyl phosphine derivative of2. Co3(CO)5(PPh3)2S (SPMe3) (2a) were determined. Compound1 contains a quasi-planar rhomboidal Co4 cluster formed by two Co3 isosceles triangles sharing a Co-Co edge. One triangle is capped by a sulfur atom, the other triangle has two edge-bridging PMe2 moieties. Electron counting gives 64 electrons corresponding to a planar system; the distribution of long Co-Co distances, in particular in the triangle bearing PMe2 bridges, suggests that the excess electrons are located on Co-Co antibonding ortibals. Compound2a contains a Co3S cluster with one side bridged by a SPMe2 unit forming a four-membered Co2SP ring. The substitution of two CO groups with two PPh3 causes a large deformation of the cluster Co-Co bondscis to these two phosphorus atoms. Crystal data for1, space group P1,a = 9.728(2) Å,b = 10.288(2) Å,c = 11.860(3) Å, = 86.41(2)°, = 76.20(2)°, = 80.37(5)°,Z = 2, 5300 reflections,R = 0.0398; for2a, space group P1,a = 9.78(3) Å,b = 13.05(4) Å,c = 18.28(6) Å, = 93.23(3)°, = 99.17(2)°, = 97.26(6)°,Z = 2, 2976 reflections,R = 0.0579. 相似文献
14.
Summary. The reaction of RuTp(COD)Cl (1) with PPh2Pri and terminal alkynes HCCR (R=C6H5, C4H3S, C6H4OMe, Fc, C6H4–Fc, C6H9) affords the neutral vinylidene complexes RuTp(PPh2Pri) (Cl)(=C=CHR) (2a–2f) in high yields. These complexes do not react with MeOH to give methoxy carbene complexes of the type RuTp(PPh2Pri)(Cl)(=C(OMe)CH2R), but react with oxygen to yield the CO complex RuTp(PPh2R)(Cl)(CO) (3). The structures of 2b, 2f, and 3 have been determined by X-ray crystallography. 相似文献
15.
O bin Shawkataly K. Ramalingam H.K. Fun A. Abdul Rahman I.A. Razak 《Journal of Cluster Science》2004,15(3):387-394
Syntheses and single crystal X-ray structures of an open triruthenium acyl carbonyl cluster [(C6H5)2SbRu3(COC6H5)(CO)10] (1) and a simple triruthenium Ru3(CO)9[(C6H5)2PCH2P(C6H5)2]Sb(C6H5)3
(2) are reported. Formation of compound (1) at room temperature from [Ru3(CO)12] and [Sb(C6H5)3] is unique, a similar reaction with Ru3(CO)10[(C6H5)2PCH2P(C6H5)2] under identical conditions results in compound (2), with Sb(C6H5)3 occupying an equatorial site. IR, 1H, 13C NMR spectra of the compounds are reported. The X-ray crystal structure of (1) consist of 2 crystallography distinct molecules and shows Ru–Sb distances in the range: 2.6361(6)–2.6273(7) Å and Ru–Ru distances in the range: 2.8236(7)–2.9855(7) Å. Ru–O distances in the bridging carbonyl are: 2.137(4), 2.158(4) Å. The Sb–Ru–Ru angles in the two molecules of the asymmetric unit are in the range of 73.78(2)–77.52° indicating the puckered nature. Compound (2) has bond parameters comparable to those of Ru3(CO)10[(C6H5)2PCH2P(C6H5)2]. The present study shows for the first time that the cleaving of Sb–C bond at room temperature is possible under non-ionic conditions, though there have been many instances of P–C and As–C bond cleavages reported previously. 相似文献
16.
Sonja Pavlik Roland Schmid Karl Kirchner Kurt Mereiter 《Monatshefte für Chemie / Chemical Monthly》2004,35(2):1349-1357
The reaction of RuTp(COD)Cl (1) with PPh2Pri and terminal alkynes HCCR (R=C6H5, C4H3S, C6H4OMe, Fc, C6H4–Fc, C6H9) affords the neutral vinylidene complexes RuTp(PPh2Pri) (Cl)(=C=CHR) (2a–2f) in high yields. These complexes do not react with MeOH to give methoxy carbene complexes of the type RuTp(PPh2Pri)(Cl)(=C(OMe)CH2R), but react with oxygen to yield the CO complex RuTp(PPh2R)(Cl)(CO) (3). The structures of 2b, 2f, and 3 have been determined by X-ray crystallography. 相似文献
17.
Sergey P. Tunik Ivan S. Podkorytov Brian T. Heaton Jonathan A. Iggo Jeyagowry Sampanthar 《Journal of organometallic chemistry》1998,550(1-2)
Multinuclear NMR data (13C, 31P, 13C–{31P}, 13C–{103Rh} and 31P–{103Rh}) for a series of mono- and di-substituted derivatives of Rh6(CO)16 containing neutral two electron donor ligands [Rh6(CO)15L, (L=NCMe, py, cyclooctene, PPh3, P(OPh)3,1/2(μ2,η1:η1-dppe)); Rh6(CO)14(LL), (LL=cis-CH2=CMe-CMe=CH2, dppm, dppe, (P(OPh)3)2)] are reported; these data show that the solid state structure is maintained in solution. Detailed assignments of the 13CO NMR spectra of Rh6(CO)15(PPh3) and Rh6(CO)14(dppm) clusters have been made on the basis 13C–{103Rh} double resonance measurements and the specific stereochemical features of the observed long range couplings in these clusters have been studied. The stereochemical dependence of 3J(P–C) for terminal carbonyl ligands is discussed and the values of 3J(P–C) are found to be mainly dependent on the bond angles in the P–Rh–Rh–C fragment; these data enable the fine structure of the complex multiplets in the 13C–{1H} and 31P–{1H} NMR spectra of Rh6(CO)14 (dppm) to be simulated. Variable temperature 13C–{1H} NMR measurements on Rh6(CO)15(PPh3) reveal the carbonyl ligands in this complex to be fluxional. The fluxional process involves exchange of all the CO ligands except the two terminal CO's associated with the rhodium trans to the substituted rhodium and can be explained by a simple oscillation of the PPh3 on the substituted rhodium atom aided by concomitant exchange of the unique terminal CO on this rhodium with adjacent μ3-CO's. 相似文献
18.
Xiao-Huan Liu Zhi-Hong Ma Li-Juan Tian Xue-Zhong Zheng Jin Lin 《Transition Metal Chemistry》2010,35(4):393-397
Abstract
Reactions of the thienyl side chain functionalized cyclopentadienyls (C4H3S)C(R1R2)C5H5[R1, R2 = CH3 (1); R1, R2 = (CH2)5 (2); R1, R2 = C2H5 (3)] with Ru3(CO)12 in refluxing xylene gave the corresponding cyclopentadienyl diruthenium carbonyl complexes [(η 5-C4H3S)CR1R2(C5H4)Ru(CO)2]2 (R1, R2 = CH3 (4); R1, R2 = (CH2)5 (5); R1, R2 = C2H5 (6)), which were characterized by elemental analysis, IR and 1H NMR spectra. The molecular structures of 4, 5 and 6 were determined by single crystal X-ray diffraction. 相似文献19.
Kumar Biradha Valerie M. Hansen Weng Kee Leong Roland K. Pomeroy Michael J. Zaworotko 《Journal of Cluster Science》2000,11(2):285-306
The structures of Os3(CO)11(PR3) with R=F, OPh, Et, p-C6H4Me, o-C6H4Me, p-C6H4(CF3) and C6H11, and with PR3=P(OCH2)3CMe have been determined. The Os–Os bond lengths in these compounds are compared to the Os–Os lengths for the other structures of Os3(CO)11(PR3) clusters reported in the literature. In most cases, the Os–Os bond length remote from the P ligand [range, 2.8666(4)–2.9044(4) Å] and that in the pseudo-trans position [range, 2.8712(5)–2.900(1) Å] show little variation as the steric and electronic properties of the P ligand are varied. The Os–Os length cis to PR3 shows more variation [range, 2.879(1)–2.9429(4) Å] and is sensitive to both the size and the -donor/-acceptor properties of the PR3 ligand: larger or better donor PR3 ligands cause an increase in the Os–Os bond length. The Os–P distances [range, 2.15(2)–2.478(1) Å] show a similar dependence on the steric and electronic properties of the PR3 ligand. 相似文献
20.
Roberto Della Pergola Elisa Brivio Luigi Garlaschelli Norberto Masciocchi Mario Manassero 《Journal of Cluster Science》1994,5(2):363-371
The phosphido-bridged cluster [Ir6(CO)14 PPh2]– has been obtained by reaction of [Ir6(CO)15]2– with PHPh2, in the presence of ferrocenium cation, followed by deprotonation. The anion was isolated as a salt of [N(PPh3)2]+ or K+ and its structure was determined by single crystal X-ray data analysis. The salt [N(PPh3)2][Ir6(CO)14PPh2] crystallizes in the triclinic space group P
witha = 11.835(1) Å,b = 15.007(1) Å,c = 18.766(2)_ Å; = 78.779(7)°, = 87.260(8)°, = 75.794(6)°,V = 3169.3(7) Å,Z = 2. The structure was solved by Direct Methods and Difference Fourier techniques and refined down toR andR
w values of 0.034 and 0.036, respectively, for 8003 observed reflections havingl > 3(I). The octahedral anion, of idealized C2 symmetry, possesses two distance Ir-P = 2.284 Å, formally acting as a three electron donor. Average bond distances (Å) and angles (degrees) are: Ir-Ir = 2.776, Ir-C
t
= 1.87, Ir-C
b
= 2.05, C
t
-O
t
= 1.14, C
b
-Ob= 1.17, Ir-P-Ir = 74.3°, Ir-C
t
-O
t
= 177°, Ir-C
b
-O
b
= 138°, Ir-C
b
-Ir = 84° (t = terminal,b = bridging). 相似文献