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1.
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   

2.
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   

3.
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   

4.
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   

5.
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.
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6.
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   

7.
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   

8.
Summary The thiolato-bridged dinuclear compounds [Rh(-SR)-(COD)]2, where R=p-C6HF4 (1),p-C6H4F (2) and CF3 (3), are obtained from the chloro-bridged analogue by ligand exchange.Compound (1) crystallizes in the space group P1 with a=9.740(3)Å, b=11.642(4)Å, c=13.997(6)Å, =103.87(3)°, =106.98(3)° and =105.10(2)°; z=2. In this dinuclear molecule both Rh atoms have a square planar coordination sharing one edge, namely the two sulphur bridging atoms. The Rh—Rh separation of 2.96 Å is consistent with at most a very weak metal-metal interaction. Upon addition of CO the dimeric [Rh(-SR)(CO)2]2 (4), (5) and (6) are obtained, but addition of PPh3 affords the monomeric species [Rh(SR)(PPh3)-(COD)] (7), (8) and (9). Reactions of the dimeric tetracarbonyl derivatives with PPh3 vary with the nature of R; [Rh(-SR)(PPh3)(CO)]2 is obtained when R=p-C6H4F (10) and CF3 (11) but monomeric [Rh(SR)-(PPh3)(CO)2] (12) is produced when R=p-C6HF4. The latter mononuclear compounds, with R=p-C6H4F (13) and CF3 (14), are also formed by reaction of [Rh(SR)-(PPh3)(COD)] with CO.  相似文献   

9.
Two new mixed metal cluster complexes PtRu3(CO)10(PPh3)(3-S)2,3 14% yield and PtRu3(CO)9(PPh3)2(3-S)2,4 23% yield were obtained from the reaction of Ru3(CO)9(3-S)2,1 with Pt(PPh3)2(C2H4) at 0°C. The cluster of4 consists of a spiked triangle of four metal atoms with two triply bridging sulfido ligands. The reaction of Ru4(CO)11(4-S)2,2 with Pt(PPh3)2(C2H4) yielded the expanded mixed-metal cluster complex PtRu4(CO)12(PPh3)(4-S)2,5 in 12% yield. The structure of the cluster5 can be described as a pentagonal bipyramid of five metal atoms and two sulfido ligands with one metal-metal bond missing. Compounds4 and5 were characterized by a single-crystal X-ray diffraction analyses.  相似文献   

10.
The reaction of the heterobinuclear metal -allenyl complexes (PPh3)2Pt(- 1: 2 , -C(R)=C=CH2)Ru(CO)Cp (R=H (1), Ph (2)) with (PPh3)AuO3SCF3 in THF at –78°C to room temperature affords the trimetallic products [(PPh3)2Pt( 2-CO)RuCpAu(PPh3)( 3- 1: 3: 1-CH2CCR)]+O3SCF– 3 (R=H (3), Ph (4)) in 46 and 55% isolated yield, respectively. The products were characterized by a combination of elemental analysis, FAB mass spectrometry, and IR and 1H, 13C, and 31P NMR spectroscopy. The structure of 4 was elucidated by a single-crystal X-ray analysis. The crystal contains discrete trimetallic RuPtAu cations and CF3SO– 3 anions. In the cation, a Pt–Ru bond of 2.7171(6) Å is supported by a semibridging CO and a CH2CCPh allyl, which is 3-bonded to Ru, and 1-bonded to each of Pt (through the CPh carbon) and Au (through the central carbon). The Ph3P–Au–C fragment is close to linear (175.0(2)°), and the coordination environment around Pt is distorted square planar. Complex 3 appears to have the same type of structure as 4 from spectroscopic data.  相似文献   

11.
In ongoing attempts to synthesize nanosized gold-platinum carbonyl phosphine clusters either directly or indirectly by initially obtaining intermediate-sized ones as potential precursors, the neutral Au–Pt CO/PR3-ligated cluster, Pt7( 2-CO)8 (PPh3)4( 4-AuPPh3)2 (1), was isolated and characterized by low-temperature CCD X-ray diffraction, IR, and mass spectrometric measurements. The heretofore unknown 9-atom metal architecture of the Au2Pt7 core may be envisioned as a Pt7 adduct of a Pt4 butterfly and an edge-opened Pt3 triangle that is additionally linked by two tetracapping AuPPh3 units. Each of the two butterfly-hinged (basal) Pt atoms is connected to two of the three edge-opened triangular Pt atoms thereby giving rise to an essentially coplanar Pt5 fragment consisting of three edge-fused bonding triangles; addition of two AuPPh3 units to the Pt7 adduct completes the Au2Pt7 framework via formation of the two symmetry-equivalent square-pyramidal ( 4-Au)Pt4 moieties, each resulting from the tetracapping of a AuPPh3 unit to the central Pt3 triangle of the coplanar Pt5 fragment and to one of the two out-of-plane wingtip Pt atoms. Six PPh3 ligands are coordinated to the two Au atoms, the two wingtip Pt atoms of the Pt4butterfly-shaped fragment, and the two outer Pt atoms of the edge-opened Pt3 triangle. Four of the eight doubly bridging 2-COs link the four edges connecting the two out-of-plane wingtip Pt atoms with the two hinged (basal) Pt atoms, while the other four 2-COs span four of the five Pt–Pt bonding edges of the coplanar Pt5 fragment (i.e., the fifth Pt–Pt bonding edge is spanned by the two out-of-plane wingtip Pt atoms). The resulting molecular configuration (without P-attached phenyl substituents) possesses crystallographic C2 (2) and pseudo-C2v symmetry. An optimized geometry of the PH3- and PMe3-models of 1, obtained from gradient-corrected (scalar-relativistic) DFT calculations is in reasonably good agreement with the crystallographically determined geometry of 1.A structure-to-synthesis approach is presented as part of extensive but unsuccessful efforts to design a high-yield reproducible preparative route to 1 in order to enable physical/chemical studies as well as to utilize it as a preformed cluster for further PPh3/CO deligation reactions.  相似文献   

12.
The reaction of Os3(CO)10(NCMe)[Si(OMe)3](-H),1, with PMe2Ph yielded the new complex Os3(CO)10(PMe2Ph)[Si(OMe)3](-H),2 by substitution of the MeCn ligand with the phosphine ligand. When heated to 125°C compound2 was decarbonylated and transformed into the new unsaturated cluster complex Os3(CO)8[-PMe2(C6H4)][Si(OMe)3](-H)2,3 in 54% yield. Compound3 was characterized by a single crystal X-ray diffraction analysis, osmium bonds. The phenyl ring of the phosphine ligand has undergoneortho-metallation by a neighboring metal atom. A terminally coordinated Si(OMe)3 ligand is coordinated to the third osmium atom. The cluster is unsaturated by the amount of 2 electrons, and there is an open coordination site on the siloxyl substituted osmium atom that is partially filled by a weak interaction with one of the -bonds of theortho-metalled phenyl ring. Complex3 reacts with CO at 1 atm to reform compound2 in 85% yield in 5 h at 40°C. Crystal Data: for3: space group = P21/n,a = 9.911(2) Å,b = 18.451(6) Å,c = 14.872(2) Å, = 95.64(2)°,Z = 4, 1994 reflections,R = 0.028.  相似文献   

13.
The thermal reactions of Ru3(CO)12 with RCOCH=CHPh (R=Me, p-MeC6H4) in hydrocarbon solvents lead to the formation of a series of complexes, several of which have been isolated as individual compounds by chromatography. The dinuclear complex Ru2(-H)(CO)6(-MeCOCH=CPh) and the tetranuclear complex Ru4(-H)(-CO)(CO)7(p-MeC 6H4 COCH=CPh)(-p-MeC6H4COCH=CPh)(4-p-MeC6H3COCH=CHPh) are characterized by an X-ray structural study. The structures of other reaction products are discussed on the basis of spectral data. The reactions are accompanied by reduction of the starting enones to the corresponding unsaturated ketones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1285–1293, July, 1993.  相似文献   

14.
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   

15.
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.
Summary Bis(cyclopentadienyl)titanium(IV) diisothiocyanate [(Cp)2-Ti(NCS)2] reacts with MCl2 (M = Cu, Pd or Pt), [CuCl(PPh3)3], [RuCl2(PPh3)3] and [RuCl2(DMSO)4] (DMSO = dimethylsulphoxide) giving solid compounds of stochiometry [(Cp)2Ti(-NCS)2MCl2] (M = Cu, Pd or Pt), [(Cp)2Ti(-NCS)2CuCl(PPh3)], [(Cp)2Ti(-NCS)2-RuCl(PPh3)2]Cl and [(Cp)2Ti(-NCS)2RuCl2(DMSO)2]. These products have been characterized by physicochemical and spectroscopic methods.  相似文献   

17.
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   

18.
Zusammenfassung Ein schnelles und einfaches Mikroverfahren zum Nachweis einiger Heteroatome organischer Verbindungen wurde entwickelt. Nach Aufschluß mit metallischem Kalium werden die entstehenden Ionen mit der Ringofenmethode getrennt und mit empfindlichen Reaktionen nachgewiesen. Nachweisgrenze: 0,5 bis 1g Stickstoff, 1 bis 2g Schwefel, 2 bis 3g Jod, 4 bis 5g Brom, 5 bis 10g Chlor in 0,5 bis 1 mg Einwaage.
Summary A rapid and simple micromethod was developed for the detection of several hetero-elements in organic compounds. After breaking down the sample with metallic potassium, the resulting ions are separated by the ring oven method and detected by means of sensitive reagents. Detection limits: 0.5 to 1g nitrogen, 1 to 2g sulfur, 2 to 3g iodine, 4 to 5g bromine, 5 to 10g chlorine in samples weighing 0.5 to 1 mg.
Résumé On a découvert un procédé à l'échelle micro, simple et rapide, pour rechercher certains hétéroéléments dans les composés organiques. Après mise en solution par le potassium métallique, on sépare les ions formés suivant la méthode du four annulaire et l'on effectue la recherche au moyen de réactions sensibles. Limite de dilution: 0,5 à 1g d'azote, 1 àg de soufre, 2 àg d'iode, 5 à 10g de chlore sur 0,5 à 1 mg de prise d'essai.
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19.
Carbonyl exchange of Fe3(3-S)2(CO)9 wioth1,1-bis(diphenylphosphino)ferrocene (dppf) in refluxing THF gives a cluster ligand with a pendant phosphine moiety, Fe3(3-S)2(CO)8 (gn1-Ph2PlC5H4)Fe(C5H4)P4 MePh2)]1 –,4. Addition of 1 to AuCl(SMe2) gives ClAu(-dppf) Fe4(3-S)2(CO)8,8 (45%). Spectroscopic evidence is also obtained for (OC)8 (3-S)2Fe3(-dppf) Os3(CO)11,7 and PdCl2[(-dppf)Fe3(3-D)2(CO)8]2,9, from1 and Os3(CO)11(CH3CN) and PdCl2CN)2, respectively. Crystal data dor3: space group P21/n,a = 10.891(3) Å,b = 19.939(3) Å,c = 20.443(2) Å, 100.17(2)°.Z = 4, 3917 reflections,R = 0.049.  相似文献   

20.
The reactions of Re2X4(-dppm)2 (X=Cl or Br; dppm=Ph2PCH2PPh2) with H2S in THF afford the dirhenium (III) complexes Re2(-H)(-SH)X4(-dppm)2, the first examples of the oxidative addition of an S-H unit across an electron-rich metal-metal triple bond. The bromide complex Re2(-H)(-SH)Br4(-dppm)2 (C2H5)2O crystallizes in the space group P21/n witha=16.631(2) Å,b=15.967(3) Å,c=19.904(2) Å, =92.698(7)°,V=5279(2) Å3, andZ=4. The structure which was refined toR=0.053 (R w=0.070) for 4903 data withI>3.0(I), shows the presence of an edge-shared bioctahedral geometry with a very short Re-Re distance of 2.4566(7) Å. While the hydrogen atoms of the -H and -SH ligands were not located in the X-ray structure determination, their presence is confirmed by IR and1H NMR spectroscopy.  相似文献   

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