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1.
Carlo Allasia Mario Castiglioni Roberto Giordano Enrico Sappa Francesco Verre 《Journal of Cluster Science》2000,11(4):493-509
The title complexes were tested in the hydrogenation of hex-3-yne and of 1,3- and 1,4-cyclohexadiene (CHD) under solid–gas conditions. The clusters were deposited on three “standard” supports, that is, pyrex glass, alumina, and silica. All the clusters, particularly (μ-H)Ru3(CO)10(PPh2), show hydrogenation activity. However, they are not particularly selective toward the formation of monoenes; “disproportionation” of 1,3- and 1,4-CHD to hydrogenated products and benzene also occurs. The hydrogenation activity of the clusters is dependent on their nature, the type of substrate, and the characteristics of the supporting material; silica and pyrex glass are usually more active than alumina. Attempts at detecting the formation of organometallic intermediates or by-products (through IR spectroscopy) were made. HRTEM was used to check for eventual decomposition on some supports. 相似文献
2.
Françoise Van Gastel Lisa Agocs Andrew A. Cherkas John F. Corrigan Simon Doherty Ravindranath Ramachandran Nicholas J. Taylor Arthur J. Carty 《Journal of Cluster Science》1991,2(2):131-136
Thecloso octahedral cluster Ru4(CO)11(μ4-PPh)(μ4-S)1 and selenium and tellurium analogues, the first examples of unsaturated ruthenium clusters with a planar metal core and different main group 15 and 16 atoms have been synthesized fromnido Ru4(CO)13(μ3-PPh). An X-ray analysis of1 and Ru4(CO)10(μ4-PPh)(μ4-Se)(PEt3)2a has confirmed thetrans disposition of phosphorus and group 16 main group fragments. 相似文献
3.
《Journal of organometallic chemistry》1995,503(2):C43-C45
Two hexaruthenium carbonyl clusters [Ru6(CO)15(μ-CO)2(μ4-NH) (μ-OMe){μ3-η2-N(H)C(O)OMe}] and [Ru6(CO)16(μ-CO)2-(μ4-NH)(μ-OMe)(μ-NCO)]2 have been isolated from the pyrolysis of H2Ru3(CO))9NOCH3, and single-crystal X-ray structure analysis shows that both 1 and 2 have a square planar arrangement of four ruthenium atoms capped by a μ4-nitrene ligand, with two additional ruthenium atoms bridging two opposite RuRu edges of the square base to form a ‘boat’ form metal framework. 相似文献
4.
《Journal of organometallic chemistry》1992,439(3):C56-C60
The purple, phosphinidene-capped, phosphido-bridged triruthenium cluster [Ru3(μ3-PPh)(μ2-PPh2)2(CO)7] reacts readily with carbon monoxide, trimethylphosphite, sodium borohydride and diphenylacetylene under mild conditions to afford product mixtures from which [Ru3(μ-PPh)(μ2-PPh2)2(CO)7+n] (n = 1, 2 or 3), [Ru3(μ3-PPh)(μ2-PPh2)2(CO)6{P(OMe)3}], [Ru3(μ3-η3-PhPCPhCPh)(μ2-PPh2)2(CO)6], respectively, can be isolated. The structure of [Ru3(μ3-PPh)(μ2-PPh2)2(CO)6{P(OMe)3}] has been established X-ray crystallographically. 相似文献
5.
Michael I. Bruce Michael Schulz Brian W. Skelton Allan H. White 《Journal of Cluster Science》2000,11(1):79-86
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
6.
The complexes Pt(nb)3-n(P-iPr3)n (n=1, 2, nb=bicyclo[2.2.1]hept-2-ene), prepared in situ from Pt(nb)3, are useful reagents for addition of Pt(P-iPr3)n fragments to saturated triruthenium clusters. The complexes Ru3Pt(CO)11(P-iPr3)2 (1), Ru3Pt(-H)(3-3-MeCCHCMe)(CO)9(P-iPr3) (2), Ru3Pt(3-2-PhCCPh)(CO)10(P-iPr3) (3), Ru3Pt(-H)(4-N)(CO)10(P-iPr3) (4) and Ru3Pt(-H)(4-2-NO)(CO)10(P-iPr3) (5) have been prepared in this fashion. All complexes have been characterized spectroscopically and by single crystal X-ray determinations. Clusters 1–3 all have 60 cluster valence electrons (CVE) but exhibit differing metal skeletal geometries. Cluster 1 exhibits a planar-rhomboidal metal skeleton with 5 metal–metal bonds and with minor disorder in the metal atoms. Cluster 2 has a distorted tetrahedral metal arrangement, while cluster 3 has a butterfly framework (butterfly angle=118.93(2)°). Clusters 4 and 5 posseses 62 CVE and spiked triangular metal frameworks. Cluster 4 contains a 4-nitrido ligand, while cluster 5 has a highly unusual 4-2-nitrosyl ligand with a very long nitrosyl N–O distance of 1.366(5) Å. 相似文献
7.
《Journal of organometallic chemistry》1992,429(3):C41-C45
The compound [Ru4(μ-Se)2(CO)8(μ3-CO)3] (1), has been obtained in good yield by vacuum pyrolysis of [RU3(CO)12] with [Ph2Se2] at 185°C. Reaction of 1 with 1,3-bis(diphenylphosphino)propane at room temperature affords the novel cluster [RU3(μ3-Se)2(CO)7(Ph2P(CH2)3PPh2)] (2). The structures of 1 and 2 have been determined by an X-ray diffraction study. 相似文献
8.
《Journal of organometallic chemistry》1990,391(2):C28-C32
Deprotonation of Ir4(CO)11PPh2H (1) in the presence of [AuPPh3][PF6] yields the novel species Ir4(CO)11(PPh2AuPPh3) (2), which possesses a tetrahedral framework bearing a terminally bound PPh2AuPPh3 ligand. When heated in toluene, 2 is converted into the phosphido species Ir4(CO)10(μ-PPh2)(μ-AuPPh3). 相似文献
9.
Ching-Juh Way Yun Chi Ipe J. Mavunkal Sue-Lein Wang Fen-Ling Liao Shie-Ming Peng Gene-Hsiang Lee 《Journal of Cluster Science》1997,8(1):87-100
Treatment of carbido cluster Ru5(μ 5-C)(CO)15 with Me3NO in acetonitrile solution followed by addition of dimethyl maleate or dimethyl acetylene dicarboxylate affords new clusters Ru5(μ 5-C)(CO)13[C2H2(CO2Me)2] (1) and Ru5(μ 5-C)(CO)15[C2(CO2Me)2] (2), respectively. Single crystal X-ray structural studies reveal that both complexes contain a wingtip-bridged butterfly pentametallic skeleton. In complex1 the maleate fragment is coordinated to one wingtip Ru atom through its carbon-carbon double bond and to the adjacent Ru atom by the formation of two O → Ru dative bonding interactions, while the acetylene dicarboxylate fragment in2 is best considered as acis-dimetallated alkene, linking one hinge Ru atom and the nearby Ru atom at the bridged position. Crystal data for1: space group P 42/n;a=20.199(6),c=13.941(3) Å,Z=8; finalR F=0.025,R w=0.026 for 3963 reflections withI>2σ(I). Crystal data for2: space group P21/n;a=9.634(3),b=20.062(6),c=17.372(5) Å,β=90.62(2)°,Z=4; finalR F=0 033,R w=0.036 for 4683 reflections withI>3σ(I). 相似文献
10.
Daniele Cauzzi Claudia Graiff Chiara Massera Giovanni Predieri Antonio Tiripicchio 《Journal of Cluster Science》2001,12(1):259-271
The reaction of [Ru3(CO)12] with Ph2(pyth)PSe (pyth=5-(2-pyridyl)-2-thienyl) allows to obtain two novel clusters [Ru3(3-Se)2(CO)7{P(pyth)Ph2}2] 1 and [Ru3(3-Se)(-PPh2)(-pyth)(CO)6{P(pyth)Ph2}] 2 in satisfactory yields. The first one exhibits the well-known bicapped, open triangular, 50-electron nido-core, whereas 2, whose crystal structure has been determined, shows the rather rare Ru3Se tetrahedron with the Ph2P and pyth fragments as side-bridging ligands. Morever cluster 2 belongs to the exiguous family of selenido-phosphido clusters not easily achievable by other routes. 相似文献
11.
《Journal of organometallic chemistry》1987,321(3):409-416
The tetranuclear ruthenium cluster [Ru4(CO)10Cl2(OEt)2] has been prepared in low yield by the reaction of [Ru3(CO)12] with [N(PPh3)2]Cl in refluxing EtOH, followed by oxidation with either [NO][BF4] or Ag[ClO4]. A single-crystal X-ray analysis of the complex shows that the four metal atoms adopt a planar geometry with one ruthenium bonded by two μ2-Cl ligands and two μ3-OEt ligands to a trinuclear fragment. This complex crystallises in the monoclinic space group I2/c, with a 14.458(3), b 22.073(6), c 15.302(4) Å, β 99.54(2)°, Z = 8; 3113 observed data with F > 3σ(F) were refined by blocked full-matrix least squares to R = 0.031, Rw = 0.034. 相似文献
12.
A new synthesis of Mo2(CO)8(-PPh2)2 and W2(CO)8(-PPh2)2 by the reaction of molybdenum and tungsten hexacarbonyls with a tetraazamacrocyclic ligand containing —CH2PPh2 side chains, comprising cleavage of the phosphorus-methylene bond has been performed. The complexes have been investigated by magnetic and spectroscopic measurements and by single-crystal structure analyses. The structural characterization of a new polymorph of Mo2(CO)8(-PPh2)2 has been described. 相似文献
13.
Michael I. Bruce Natasha N. Zaitseva Brian W. Skelton Allan H. White 《Journal of Cluster Science》1996,7(2):109-119
The reaction between Ru3(3-2-PhC2C=CPh)(-dppm)(CO)8 and Co2(CO)8 afforded dark red Co2Ru3(4-C2Ph)(3-C2Ph)(-dppm)(-CO)2(CO)9, shown by an X-ray structure determination to contain a strongly twisted Co2Ru3 bow-tie cluster (central Co), to which two PhC2 units derived from cleavage of the original diyne are attached. One a these is strongly interacting with four metal atoms, the other being attached in the familiar 1,22-mode. The dppm ligand remains bridging two of the Ru atoms. 相似文献
14.
15.
Elisa Brivio Alessandro Ceriotti Roberto Della Pergola Luigi Garlaschelli Mario Manassero Mirella Sansoni 《Journal of Cluster Science》1995,6(2):271-287
Redox condensation of [Ru3H(CO)11]- with Ni(CO)4, in tetrahydrofuran solution, under a nitrogen atmosphere, yields the tetranuclear anion [NiRuH(CO)11)-. Subsequent deprotonation with Bu'OK in acetonitrile solution leads to the formation of the related dianion. Both anions have been characterized by spectroscopic techniques, elemental analysis and single crystal X-ray diffraction. [PPh4][NiRu3H(CO)12] crystallizes in the triclinic space group PI with unit cell dimensionsof a = 11.842(2) Å,b = 12.335(3) Å, c = 13.3080) Å,a = 91.89(2)°, = 93.35(1)°,y = 96.41(2)°, Z = 2, V= 1926.9(7) Å'. The NiRu3, metal core of the molecule defines a distorted tetrahedron with nine terminal and three edge bridging carbonyl groups. The hydrido ligand was located by difference Fourier techniques and was found to bridge the NiRu2 basal triangle at a distance of 0.88(6) A from this plane. Selected average distances and angles are: Ru-Ru = 2.839 Å, Ru-Ni = 2.640 Å, Ru-C, = 1.910 A,Ru-C
b
= 2.084 Å, Ni-C
b
= 2.022 Å, Ru-H = 1.77 Å, C-0, = 1.135 Å, C-O
b
= 1.159 Å, M-C-O, = 176.3°,M-C--O
b
= 139.3°;other distances are: Ni-C1 = l.758(7) Å, Ni-H= 1.85(7) Å. [NEt4]2[NiRu3(CO)12] crystallizes in the orthorhombic space group Pnma (no. 62) with unit cell dimensions ofa=20.247(5) Å,b = 15.038(4)Å,c = 12.079(3) Å, Z=4, V=3678(2) A'. The molecule contains a tetrahedral NiRu3 core with eight terminal and four edge bridging carbon monoxide groups which bridge the three Ni-Ru and one Ru-Ru bond. Average distances and angles are: Ru -Ru =2.3050A Ru-Ni 2.648 Å, Ru-C
t
= 1.878 Å, Ru-C
b
2.045 Å, Ni-C
b
= 2.055 Å, C-O
t
= 1.145 Å, C-01,=1.157 Å, M-C-O,= 176.9°, M-C-O
b
= 138.6°; other distance is: Ni-C
t
= 1.754(10) Å,t = terminal,b = bridging. 相似文献
16.
The reaction of μ-alkyne-bridged dimolybdenum compound [Mo2(μ-C2HPh)(CO)4(η5-C5H4C(O)Me)2] 1 with Co2(CO)8 in refluxing toluene gave a new butterfly compound [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2] 2 which was fully characterized by elemental analysis, IR, 1H NMR and X-ray single crystal diffraction techniques. 2 crystallized in monoclinic system, C30H20Co2Mo2O10, Mr=850.23, space group P21/a(#14), a=14.165(5), b=12.498(2), c=16.204(2)(A), β = 96.50(2)°, V = 2850(1)(A)3, Z = 4, Dc = 1.981 g cm-3, F(000)=1672, μ(MoKα)=20.41 cm-1, final R=0.030, Rw=0.039 for 4831 observable reflections with I>2σ(I). The structure contains a Co2Mo2 butterfly core, and each Mo-Co bond is spanned by an asymmetric semi-bridging carbonyl ligand. 相似文献
17.
《Journal of Coordination Chemistry》2012,65(3):229-244
Abstract [Cp2Fe2(CO)2(μ-CO)(μ-CHP(OPh)3)+][BF? 4] crystallizes in the centrosymmetric monoclinic space group P21/n with a = 12.553(7) Å, b = 16.572(11) Å, c = 15.112(8) Å, β = 100.00(4)°, V = 3096(3) Å3 and D(calcd.) = 1.579 g/cm3 for Z = 4. The structure was refined to R(F) = 5.83% for 1972 reflections above 4σ(F). The cation contains two CpFe(CO) fragments linked via an iron—iron bond (Fe(1)—Fe(2) = 2.544(3)Å), a bridging carbonyl ligand (Fe(1)—C(4) = 1.918(1) Å, Fe(2)—C(4) = 1.946(12)Å) and a bridging CHP(OPh)3 ligand (Fe(1)—C(1) = 1.980(9)Å, Fe(2)—C(1) = 1.989(8)Å). Distances within the μ-CHP(OPh)3 moiety include a rather short carbon—phosphorus bond [C(1)—P(1) = 1.680(10)Å] and P—O bond lengths of 1.550(7)–1.579(6)Å. The crystal is stabilized by a network of F…H—C interactions involving the BF? 4 anion. [Cp2Fe2(CO)2(μ-CO)(μ-CHPPh3)+][BF? 4], which differs from the previous compound only in having a μ-CHPPh3 (rather than μ-CHP(OPh)3) ligand, crystallizes in the centrosymmetric monoclinic space group P21/c with a = 11.248(5)Å, b = 13.855(5)Å, c = 18.920(7)Å, β = 96.25(3)°, V = 2931(2)Å3 and D(calcd.) = 1.559 g/cm3 for Z = 4. This structure was refined to R(F) = 4.66% for 1985 reflections above 4σ(F). Bond lengths within the dinuclear cation here include Fe(1)-Fe(2) = 2.529(2)Å, Fe(1)—C(3) = 1.904(9) Å and Fe(2)—C(3) = 1.911(8) Å (for the bridging CO ligand) and Fe(1)—C(1P) = 1.995(6) Å and Fe(2)—C(1P) = 1.981(7) Å (for the bridging CHPPh3 ligand). Distances within the μ-CHPPh3 ligand include a longer carbon—phosphorus bond [C(1P)—P(1) = 1.768(6)Å] and P(1)—C(phenyl) = 1.797(7)–1.815(8) Å. 相似文献
18.
Chris J. Adams Michael I. Bruce Brian W. Skelton Allan H. White 《Journal of Cluster Science》1992,3(2):219-227
The reaction between Ru5(5-C2PPh2)(-PPh2)(CO)13 and Au(C2Ph)(PPh3) afforded AuRu5(5-C2PPh2)(-C2Ph)(-PPh2)(CO)13 (PPh3), in which the Ru5 cluster has a scorpion geometry; the Au(PPh3) group bridges one of the Ru-Ru bonds of the Ru3 triangle, while the C2Ph group bridges one of the tail Ru-Ru vectors.For Part 84, see Ref. 1. 相似文献
19.
《Journal of organometallic chemistry》1989,377(1):C35-C39
Reaction of [Ru3(CO)12] with a two molar proportion of (RO)2PN(Et)P(OR)2 (R = Me or Pri) in benzene under reflux affords a number of products including [Ru3(CO)10{μ-(RO)2PN(Et)P(OR)2}], [Ru3(CO)9{μ-(RO)2PN(Et)P(OR)2}{η1-(RO)2PN(Et)P(OR)2}] and, as the major species, the tetranuclear derivative [Ru4(μ3-η2-CO)(CO)9{μ-(RO)2PN(Et)P(OR)2}2]. An X-ray diffraction study of [Ru4(μ3-η2-CO)(CO)9{μ-(MeO)2PN(Et)P(OMe)2}2] has revealed that the skeletal framework adopts a butterfly structure and that one of the carbonyl groups functions as a triply bridging four-electron donor ligand capping the two wing-tip and one of the hinge ruthenium atoms. 相似文献
20.
《Journal of organometallic chemistry》1990,393(2):C30-C33
The reactions of [Ru3(μ-H)(μ-ampy)(CO)9] (1) (Hampy = 2-amino-6-methylpyridine) with one or two equivalents of PPh2H lead to the complexes [Ru3(μ-H)(μ3-ampy)(CO)8(PPh2H)] (2) or [Ru3(μ-H)(μ3-ampy)(CO)7(PPh2H)2] (3), in which the PPh2H ligands are cis to the bridging NH fragment and cis to the hydride. Complex 2 can be transformed in refluxing THF into the phosphido-bridged derivative [Ru3(μ3-ampy)(μ-PPh2)(μ-CO)2(CO)6] (4), which contains the PPh2 ligand spanning one of the two RuRu edges unbridged by the amido moiety, and presents an extremely high 31P chemical shift of 386.9 ppm. Under similar conditions, complex 3 gives a mixture of two isomers of [Ru3(μ-H)(μ3-ampy)(μ-PPh2)2(CO)6] in a 5:1 ratio; the major product (5) has a plane of symmetry, whereas the minor one (6) is asymmetric. 相似文献