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1.
《Journal of organometallic chemistry》1986,307(3):C55-C57
RuHCl(PPh3)3 reacts quantitatively with cycloheptatriene in CH2Cl2 at 35°C in 15 min to give Ru(η5-C7H9)Cl(PPh3)2 and PPh3. The major isomer adopts a conformation with inequivalent phosphorus ligands and no plane of symmetry through the C7H9 ligand, but rapid intramolecular scrambling with δG3 = 10.6 kcal mol−1 results in an averaged 1H, 13C, and 31P NMR spectrum at room temperature. RuHCl(PPh3)3 reacts with cyclohepta-1,3-diene to give initially Ru(η3-C7H11)Cl(PPh3)2, but in a subsequent reaction this is dehydrogenated to give Ru(η5-C7H9)Cl(PPh3)2. 相似文献
2.
A. A. Koridze Y. I. Zdanovich N. V. Andrievskaya Yu. Siromakhova P. V. Petrovskii M. G. Ezernitskaya F. M. Dolgushin A. I. Yanovsky Yu. T. Struchkov 《Russian Chemical Bulletin》1996,45(5):1200-1206
Diyne FcCmCC.CFc (Fc is ferrocenyl) reacts with Ru3(CO)12 in boiling hexane to yield binuclear complexes Ru2 and Ru2(CO)6(C4Fc2(C=CFc)2C=O) containing ruthenacyclopentadiene and diruthenacycloheptadienone rings, respectively. The isomerism of the complexes is due to the different ways of coupling of the alkyne fragments of the diyne, namely, head-to-head, head-to-tail or tail-to-tail. The reaction of enyne PhC=CCH=CHPh with Ru3(CO)12 under similar conditions gives isomeric binuclear complexes Ru2(CO)6(C4Ph2(CH=CHPh)2) and trinuclear clusters Ru3(CO)6(w-CO)2(C4Ph2(CH=CHPh)2) and Ru3(CO)8(3-,1-1-4-2 C4Ph2(CH=CHPh)2). The structure of the latter was determined by X-ray diffraction analysis. The Ru3 triangle coordinates eight terminal CO groups and the organic ligand resulting from the head-to-head dimerization of enyne molecules; the ruthenacyclopentadiene moiety is 4-coordinated to the Ru(CO)2 group, and the third ruthenium atom is 2-bound to one of the PhCH=CH groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1261–1267, May, 1996. 相似文献
3.
Dr. Anne-Frédérique M. Pécharman Erika M. Roberts Dr. Fedor M. Miloserdov Dr. Victor Varela-Izquierdo Dr. Mary F. Mahon Prof. Michael K. Whittlesey 《欧洲无机化学杂志》2023,26(12):e202300037
Addition of an excess of ZnMe2 to a mixture of [Ru(PPh3)3HCl] and IMes (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) yields the bis-cyclometallated complex, [Ru(IMes)“(PPh3)2] 2 , together with the mono-cyclometallated, Ru−Zn heterobimetallic complex [Ru(IMes)′(PPh3)2(ZnMe)] 3 . Treatment of 2 with H2, PhSiH3 or pinacolborane yields the previously reported complex, [Ru(IMes)′(PPh3)2H] 1 , the synthesis of which has been reinvestigated. Further studies of small molecule reactivity show that 1 adds H2 to give [Ru(IMes)(PPh3)2H4] 4 , whilst 2 reacts with catecholborane to give [Ru(IMes-Bcat)′(PPh3)2H] 5 , in which (IMes-Bcat)′ signifies a borylated NHC ligand that is singly-metallated onto Ru. Treatment of 2 with CO gives the 18-electron dicarbonyl product [Ru(IMes)”(PPh3)(CO)2] 6 . Compounds 1 – 3 , 5 and 6 have been structurally characterised. 相似文献
4.
The electron distributions and bonding in Ru3(CO)9(
3-
2,
2,
2-C6H6) and Ru3(CO)9(
3-
2,
2,
2-C60) are examined via electronic structure calculations in order to compare the nature of ligation of benzene and buckminsterfullerene to the common Ru3(CO)9 inorganic cluster. A fragment orbital approach, which is aided by the relatively high symmetry that these molecules possess, reveals important features of the electronic structures of these two systems. Reported crystal structures show that both benzene and C60 are geometrically distorted when bound to the metal cluster fragment, and our ab initio calculations indicate that the energies of these distortions are similar. The experimental Ru–Cfullerene bond lengths are shorter than the corresponding Ru–Cbenzene distances and the Ru–Ru bond lengths are longer in the fullerene-bound cluster than for the benzene-ligated cluster. Also, the carbonyl stretching frequencies are slightly higher for Ru3(CO)9(
3-
2,
2,
2-C60) than for Ru3(CO)9(
3-
2,
2,
2-C6H6). As a whole, these observations suggest that electron density is being pulled away from the metal centers and CO ligands to form stronger Ru–Cfullerene than Ru–Cbenzene bonds. Fenske-Hall molecular orbital calculations show that an important interaction is donation of electron density in the metal–metal bonds to empty orbitals of C60 and C6H6. Bonds to the metal cluster that result from this interaction are the second highest occupied orbitals of both systems. A larger amount of density is donated to C60 than to C6H6, thus accounting for the longer metal–metal bonds in the fullerene-bound cluster. The principal metal–arene bonding modes are the same in both systems, but the more band-like electronic structure of the fullerene (i.e., the greater number density of donor and acceptor orbitals in a given energy region) as compared to C6H6 permits a greater degree of electron flow and stronger bonding between the Ru3(CO)9 and C60 fragments. Of significance to the reduction chemistry of M3(CO)9(
3-
2,
2,
2-C60) molecules, the HOMO is largely localized on the metal–carbonyl fragment and the LUMO is largely localized on the C60 portion of the molecule. The localized C60 character of the LUMO is consistent with the similarity of the first two reductions of this class of molecules to the first two reductions of free C60. The set of orbitals above the LUMO shows partial delocalization (in an antibonding sense) to the metal fragment, thus accounting for the relative ease of the third reduction of this class of molecules compared to the third reduction of free C60. 相似文献
5.
《Journal of organometallic chemistry》1989,367(3):C21-C24
The radical cations [Mo(CCR)(dppe)(η-C7H7)]+ (R = Ph or Bun); dppe = Ph2PCH2CH2PPh2) undergo coupling at Cβ of the alkynyl ligand to afford the divinylidene-bridged, dimeric products [Mo2(dppe)2(η-C7H7)2(μ-C4R2)]2+, characterised crystallographically for R = Ph. 相似文献
6.
R. G. Gasanov M. V. Tsikalova E. V. Martynova Yu. N. Novikov 《Russian Chemical Bulletin》2008,57(2):309-315
Addition of the ·P(O)(OPri)2, Me·, Et·, ·But, and Cl3C· radicals to the (ν2-C60)Os(CO)-(PPh3)2(CNBut) complex (1) was studied by ESR spectroscopy. The spectral parameters of the spin-adducts of these radicals with complex 1 were determined. The predominant direction of the attack by the ·P(O)(OPri)2, ·But, and Cl3C· radicals are the cis-1 and cis-2 bonds of the fullerene molecule. The stability of the spin-adducts depends substantially on the nature of the added radical.
The addition rate constants of the ·P(O)(OPri)2, ·But, and Cl3C· radicals to complex 1 and the dimerization rate constants for these spin-adducts were determined.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 301–307, February, 2008. 相似文献
7.
Rainer Bartsch Christian Müller Axel Fischer Peter G. Jones 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Syntheses and structures of penta- and hexaphosphorus analogues of ferrocene have been described recently1. Unlike their simple ferrocene analogues, these complexes have further ligating potential towards other transition metal centres by virtue of the availability of the ring phosphorus lone-pair electrons that are not involved in the η5-coordination. We now describe the first examples of coordination compounds of the triphospha-ferrocene [Fe(η5-C5Me5) (η5-C2 tBu2P3]. In the ruthenium complex [Fe(η5-C5Me5)(η5-C2 tBu2P3) Ru3(CO)9] 2 two adjacent phosphorus atoms of the η5-C2 tBu2P3 ring are interlinked by a ruthenium carbonyl cluster in which all three ruthenium atoms interact with the phosphorus atoms. The tetrametallic nickel complex [Fe(η5-C5Me5)(η5-C2 tBu2P3)Ni(CO)2]2 3 represents the first example of intermolecular interlinkage of two phospha-ferrocene systems by two metal centres. 相似文献
8.
The substituted sandwich complex crystallizes in monoclinic space groupP21/m withZ=2. Twinning to the (001) direction with the special conditionc
*/4a
* = cos
* causes systematic superposition of the reciprocal lattices of both domains and results in an apparent unit cell with double volume and the reflection condition (2h)kl, l=2n. The structure solution was obtained with the subset of intensity data for the predominant individuum and converged atR = 0.040,R
w
=0.046 for 832 independent observations and 122 variables. The molecules show disorder with respect to the crystallographic mirror plane. The structure is closely related to that of decamethylruthenocene. 相似文献
9.
The clusters Fe3(CO)9(RC2
R
1) (R=R
1=Ph, Et; R=Me, R
1=Ph), complexes 1a, 1b, 1c, containing an alkyne bound in perpendicular fashion with respect to a cluster edge, catalyze the hydrogenation of some acetylenes either under homogeneous and solid–gas conditions. We hypothesize that cluster catalysis occurs and that the catalytic activity is related to the coordinating ability of the alkynic substrates. Competition between hydrogenation and formation of metallacyclic byproducts occurs. The new metallacyclic derivatives Fe3(CO)6(-CO)2{(RC2
R
1)(R
2C2
R
3)}, Fe2(CO)6{(RC2
R
1)(R
2C2
R
3)} {R=R
1=Et, R
2=R
3=H, Ph; R
2=Me, R
3=Et, Ph; R
2=H, R
3=Bu
t
. R=R
1=Ph, R
2=Me, R
3=Et, Ph} (complexes 2, 3) were found both in the homogeneous reaction mixtures and after the solid–gas reactions. The formation of these products lowers the catalytic activity. 相似文献
10.
T. Yu. Orlova Yu. S. Nekrasov P. V. Petrovskii M. G. Ezernitskaya Z. A. Starikova O. L. Lependina 《Russian Chemical Bulletin》2008,57(1):63-67
The metallation of the η5-C5H5(CO)2Fe-η1,η5-C5H4Mn(CO)3 complex with BunLi (THF, ?78 °C) followed by the treatment of the lithium derivative with Ph2PCl afforded the η5-Ph2PC5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3 complex. The reaction of the latter with η5-C5H5(CO)3WCl in the presence of Me3NO produced the trinuclear complex η5-C5H5Cl(CO)2W-η1,η5-(Ph2P)C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3. The structure of the latter complex was established by IR, UV, and 1H and 31P NMR spectroscopy and X-ray diffraction. The reaction of MeSiCl3 with three equivalents of LiC5H4(CO)2Fe-η1,η5-C5H4Mn(CO)2PPh3 gave the hexanuclear complex MeSi[C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)2PPh3]3. 相似文献
11.
Synthesis of Co3(CO)7(μ-η3-Allyl)(μ3-X) Complexes (X=S, Se) and Structure of the Selenium Derivative
László Markó Giuliana Gervasio Domenica Marabello Gá Szalontai 《Journal of Cluster Science》2000,11(1):29-38
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
12.
Paul R. Raithby Jack Lewis Catherine A. Morewood M. Carmen Ramirez de Arellano Gregory P. Shields 《Journal of Cluster Science》2006,17(1):13-26
Thermolysis of [Ru3(CO)12] in cyclohexene for 24 h affords the complexes [Ru(CO)3(η4-C6H8)] (1), [Ru3H2(CO)9(μ2-η1:η2:η1-C6H8)] (2), [Ru4(CO)12(μ4-C6H8)] (3) [Ru4(CO)9(μ4-C6H8)(η6-C6H6)] (4a and 4b, two isomers) and [Ru5(CO)12(μ4-η2-C6H8)(η4-C6H8)] (5), where 1, 3, 4a and 4b have been previously characterised as products of the thermolysis of [Ru3(CO)12] with cyclohexa-1,3-diene. The molecular structures of the new clusters 2 and 5 were determined by single-crystal X-ray crystallography, showing that two conformational polymorphs of 5 exist in the solid state, differing in the orientation of the cyclohexa-1,3-diene ligand on a ruthenium vertex. 相似文献
13.
《Journal of organometallic chemistry》1986,303(3):417-427
Further studies of the reactions between ruthenium σ-acetylide complexes and electrophilic olefins CHArC(CN)(X) (Ar = C6H4NO2-4, Ph; X = CN; Ar = C6H4NO2-4, X = CO2Et) have shown the formation of allylic, butadienyl, and in one case, cyclobutenyl complexes. The direction of addition is such that the =C(CN)(X) group becomes attached to the α-carbon of the acetylide. This is confirmed by the X-ray structure of Ru{C[C(CN)2]CPhCH(C6H4NO2-4)}(dppe)(η-C5H5) · 0.5CH2Cl2, cr with cell dimensions a 28.81(1), b 9.661(2), c 30.782(8) Å, β 95.02 (3)°, and Z = 8. The structure was refined by a least-squares procedure with the use of 4291 statistically significant reflections [I > 2.5σ(I)] to R 0.075 and Rw 0.076. 相似文献
14.
富勒烯配合物η2-C60[Ru(NO)(PPh3)]2的合成与表征 总被引:4,自引:0,他引:4
从1985年Kroto等[1]发现富勒烯至今, 其在化学、材料和物理等领域已有较多的研究[2~8]. 目前有关C60取代的金属小分子配合物(如羰基、亚硝酰基等)的研究方兴未艾. 而以NO为配体的亚硝酰基金属富勒烯配合物仅有数例[2,3], Green等[3]在研究以CO和NO为配体的金属富勒烯系列化合物的合成中, 认为C60不能与Ru(NO)2(PPh3)2发生反应. 本文利用Ru(NO)2(PPh3)2与C60反应首次合成出η2-C60[Ru(NO)(PPh3)]2配合物, 并对其进行了表征. 相似文献
15.
O. A. Kizas V. V. Krivykh V. V. Vorontsov A. A. Koridze 《Russian Chemical Bulletin》1993,42(6):1102-1103
Protonation of triosmium clusters Os3(-H)(CO)9(3-,2-CC-R) (R=CMe2OH, C(Me)=CH2) affords a cationic complex containing a six-electron propargyl ligand which has been detected for the first time.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1144–1145, June, 1993. 相似文献
16.
《Journal of organometallic chemistry》1986,310(3):C66-C68
The synthesis and characterization of optically active olefinic complexes of the type [(η-C5H5)Ru{Ph2PCH(CH3)CH2PPh2}(CH2CHR″)]PF6 (R″ H, CH3, C6H5, COOCH3), in which the metal is a stereogenic center, are reported. The enantioface discrimination of the prochiral olefin is influenced by the chiral ligand and by the stereogenic metal atom. The chiral center at the metal appears to be optically labile. The rates of the epimerization at the metal and of the olefin enantioface depend on the structure of the coordinated olefin. 相似文献
17.
《Journal of organometallic chemistry》1989,372(2):C15-C18
The thermal reaction of Ru3(CO)9(PPh3)3 with precursors (HL) of binucleating anionic ligands affords the ruthenium(I) dimers Ru2(μ-L)2(CO)4(PPh3)2 (3), t-butylmercaptane (4); H2L2 = 1,8-diaminonaphthalenene (5)]. The crystal structure of complex 5 shows that each nitrogen of the 1,8-diiminonaphthalene ligand bridges the two ruthenium atoms, leading to a vary distorted, octahedral arrangement of the ligands and a very short RuRu distance, 2.5788(3) Å. 相似文献
18.
《Journal of organometallic chemistry》1986,299(3):C51-C55
The coupling of [Ru(CO)2L(η4-cot)] (L = CO or PPh3, cot = cyclooctatetraene) with [Fe(CO)3(η5-cyclohexadienyl)]+ or [Fe{P(OMe)3}(NO)2(η3-allyl)]+ yields respectively the dimetallic species [Ru(CO)2L(η2,η3-C8H8{Fe(CO)3(η4-C6H7)}] (3) and the allyl-substituted derivative [Ru(CO)2L(η5-C8H8CH2C(Me)CH2)][PF6] (5) whose X-ray structure is reported; paramagnetic [Co(η-C5H5)2] and [Ru(CO)3(η5-cyclohexadienyl)]+ give diamagnetic [Ru(CO)3(η4-C6H7C5H6(o-C5H5)] (8) via CC bond formation and one-electron reduction. 相似文献
19.
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
20.
《Journal of organometallic chemistry》1986,301(2):145-151
Ph3GeSiMe3 and Ph3GeSiMe2Fe(CO)2(η5-C5H5) have been synthesized and their crystal structures determined. The GeSi bond in iron (2.405(2) Å) is longer by 0.021 Å than in the simple germylsilane (2.384(1) Å). The significant shortening of the SiFe bond (2.328(1) Å) in the iron complex compared to that in the analogous Ph3SiSiMe2Fe(CO)2(η5-C5H5) (2.346(1) Å) and spectroscopic data indicate an enhanced SiFe interaction. 相似文献