共查询到20条相似文献,搜索用时 17 毫秒
1.
《Journal of organometallic chemistry》1986,310(2):C36-C38
The cationic [FeL(dppm)(CNPh)3]n+ (1a: L = I, n = 1; 1b: L = CNPh, n = 2) are readily deprotonated by KOH to give [FeL(dppm-H)(CNPh)3]n−1 (2a and 2b). 2a reacts with [thtAuPPh3]PF6 to give mer-[FeI((PPh2)2C(H)(AuPPh3))-(CNPh)3]PF6 (3). The new heterotrimetallic species [FeL((PPh2)2C(AuPPh3)2)-(CNPh)3]n+ (4a and 4b) have been obtained from 1a and 1b by treatment with ClAuPPh3 in the presence of KOH. 相似文献
2.
Friedrich Schoder Ulrike Plaia Robert Metzner Wilfried Sperber Wolfgang Beck Wolf Peter Fehlhammer Prof. Dr. 《无机化学与普通化学杂志》2010,636(5):700-709
The reactions of [Re(CO)6]+, [FeCp(CO)2CS]+ and [FeCp(CNPh)3]+ with the metallo nitrile ylides [M–{C+=N–C–(H)CO2Et}(CO)5]– (M = Cr, W) and the chromio nitrile imine [Cr–{C+=N–N–H}(CO)5]– (generated by mono‐α‐deprotonation of the parent isocyanide complexes) to give neutral 5‐metallated 1,3‐oxazolin‐ ( 1 ), 1,3‐thiazolin‐ ( 2 ), imidazolin‐ ( 3 , 4 ), 1,3,4‐oxdiazolin‐ ( 5 ), 1,3,4‐thiadiazolin‐ ( 6 ) and 1,3,4‐triazolin‐2‐ylidene ( 8 ) chromium and tungsten complexes represent the first all‐organometallic versions of Huisgen’s 1,3‐dipolar cycloadditions. The formation of 6 and 8 is accompanied by partial decomposition to (OC)5Cr–C≡N–FeCpL2 {L = CO ( 7 ), CNPh ( 9 )}. The structures of 4a and 5 have been characterized by X‐ray diffraction. 相似文献
3.
Corry Decker 《Journal of organometallic chemistry》2004,689(9):1691-1701
The reactions of [Fe3(CO)12] or [Ru3(CO)12] with RNC (R=Ph, C6H4OMe-p or CH2SO2C6H4Me-p) have been investigated using electrospray mass spectrometry. Species arising from substitution of up to six ligands were detected for [Fe3(CO)12], but the higher-substituted compounds were too unstable to be isolated. The crystal structure of [Fe3(CO)10(CNPh)2] was determined at 150 and 298 K to show that both isonitrile ligands were trans to each other on the same Fe atom. For [Ru3(CO)12] substitution of up to three COs was found, together with the formation of higher-nuclearity clusters. [Ru4(CO)11(CNPh)3] was structurally characterised and has a spiked-triangular Ru4 core with two of the CNPh ligands coordinated in an unusual μ3-η2 mode. 相似文献
4.
Three series of cationic manganese(I) carbonyls are reported: [Mn(CO)5-n(CNMe)n(CNPh)]PF6 (n = 1 → 4), [Mn(CO)5-n(CNMe)(CNPh)n]PF6 (n = 1 → 4), and [Mn(dpe)(CO)4-n(CNMe)n]PF6 (n = 1 → 4). Most of these compounds were prepared from a substituted metal carbonyl halide by replacement of halide ion by an added ligand (CNR or CO), such reactions requiring an added halide ion acceptor (Ag+ or AlCl3). The added ligand enters the site of departing halide ion. It was possible to prepare isomers of many compounds reported, taking advantage of this stereospecificity. Structures of the products were defined, often unequivocally, by infrared and nmr spectroscopic data. Cyclic voltammetry showed that these compounds undergo one electron oxidations, the ease of oxidation determined by the nature of the ligand groups and the stereochemistry. 相似文献
5.
Summary Monocarbonyls of manganese(I) with two chelating diphosphinestrans-[Mn(CO)(diphos)2(L)]A, [diphos = 1,2-bis(diphenylphosphino)ethane, dppe, or bis(diphenylphosphino)methane, dppm; L=nitriles, NCR (NCMe, NCEt, NCPh, or NCCH2Ph), dinitriles, NCGCN (NCCH2CN, NCCH2CH2CN, oro-(NC)2C6H4), isonitriles, CNR, (CNPh, or CNBut); A = C1O
4
–
or PF
6
–
],trans-[(Mn(CO)(dppm)2)2(-NCCH2CH2CN)](ClO4)2 and the monocarbonyl with one diphosphine,mer-[Mn(CO)(dppe)(CNBut)3]ClO4, have been prepared fromtrans-[Mn(CO)(diphos)2Br].In this paper we have adopted the convention that gives positive shift to signals at higher frequency of ext. H3PO4. 相似文献
6.
《Journal of Inorganic and Nuclear Chemistry》1981,43(10):2349-2353
The complexes W(CO)2(PPh3)(q)2, W(CO)2(PPh3)(pic)2 and W(CO)2(PPh3)(dsp) (where Ph = C6H5, q− = 8-quinolinolato, pic− = picolinato, and dsp2− = the anion of the Schiff-base N,N′-disalicylidene-1,2-phenylene-diamine) have been synthesized. The physical properties of these complexes are indicative of seven-coordinate mixed-ligand tungsten(II) chelates. W(CO)2(PPh3)(pic)2 is the most photochemically reactive and W(CO)2(PPh3)(q)2 is the most thermally reactive. Evidence that the steric effects of the quadriadentate dsp2− ligand cause a change in the overall seven-coordinate sterochemistry is presented. 相似文献
7.
Jaros?aw HandzlikTeresa Szymańska-Buzar 《Polyhedron》2012,31(1):622-631
The activation of the Ge-H bond and the formation of several hydride complexes, characterized by high-field resonances, have been detected during the 1H NMR spectroscopy monitoring of the photochemical reaction of Et3GeH and Et2GeH2 with W(CO)6 and the norbornadiene complex [W(CO)4(η4-nbd)]. The activation of the Ge-H bond of triethylgermane in the photochemical reactions of tungsten(0) complexes has been applied in the hydrogermylation of norbornadiene (nbd), which leads to the formation of endo-triethylgermylnorbornene as the major product. The complex [{W(μ-η2-H-GeEt2)(CO)4}2] has been fully characterized by NMR spectroscopy and by a single-crystal X-ray diffraction study. Evidence for the hydride ligand of the W(μ-η2-H-GeEt2) group has been provided by 1H NMR spectroscopy (δ = −9.02, 1JH-W = 31 Hz) and by DFT calculations. A DFT study of the structural properties and 1H NMR chemical shifts of several possible intermediate σ and hydride complexes formed during the photochemical reaction of W(CO)6 and Et2GeH2 has been performed. 相似文献
8.
Markus Stubenhofer Dipl.‐Chem. Christian Kuntz Dr. Michael Bodensteiner Dipl.‐Chem. Ulrich Zenneck Prof. Dr. Marek Sierka Dr. Manfred Scheer Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(25):7488-7495
Photolysis of [Cp*As{W(CO)5}2] ( 1 a ) in the presence of Mes*P?PMes* (Mes*=2,4,6‐tri‐tert‐butylphenyl) leads to the novel 1,3‐diphospha‐2‐arsaallyl radical [(CO)5W(μ,η2:η1‐P2AsMes*2)W(CO)4] ( 2 a ). The frontier orbitals of the radical 2 a are indicative of a stable π‐allylic system that is only marginally influenced by the d orbitals of the two tungsten atoms. The SOMO and the corresponding spin density distribution of the radical 2 a show that the unpaired electron is preferentially located at the two equivalent terminal phosphorus atoms, which has been confirmed by EPR spectroscopy. The protonated derivative of 2 a , the complex [(CO)5W(μ,η2:η1‐P2As(H)Mes*2)W(CO)4] ( 6 a ) is formed during chromatographic workup, whereas the additional products [Mes*P?PMes*{W(CO)5}] as the Z‐isomer ( 3 ) and the E‐isomer ( 4 ), and [As2{W(CO)5}3] ( 5 ) are produced as a result of a decomposition reaction of radical 2 a . Reduction of radical 2 a yields the stable anion [(CO)5W(μ,η2:η1‐P2AsMes*2)W(CO)4]? in 7 a , whereas upon oxidation the corresponding cationic complex [(CO)5W(μ,η2:η1‐P2AsMes*2)W(CO)4][SbF6] ( 8 a ) is formed, which is only stable at low temperatures in solution. Compounds 2 a , 7 a , and 8 a represent the hitherto elusive complexed redox congeners of the diphospha‐arsa‐allyl system. The analogous oxidation of the triphosphaallyl radical [(CO)5W(μ,η2:η1‐ P3Mes*2)W(CO)4] ( 2 b ) also leads to an allyl cation, which decomposes under CH activation to the phosphine derivative [(CO)5W{μ,η2:η1‐P3(Mes*)(C5H2tBu2C(CH3)2CH2)}W(CO)4] ( 9 ), in which a CH bond of a methyl group of the Mes* substituent has been activated. All new products have been characterized by NMR spectrometry and IR spectroscopy, and compounds 2 a , 3 , 6 a , 7 a , and 9 by X‐ray diffraction analysis. 相似文献
9.
Glenna So‐Ming Tong Dr. Chi‐Ming Che Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(29):7225-7237
We herein report a theoretical analysis based on a density functional theory/time‐dependent density functional theory (DFT/TDDFT) approach to understand the different phosphorescence efficiencies of a family of cyclometalated platinum(II) complexes: [Pt(NCN)Cl] ( 1 ; NCN=1,3‐bis(2‐pyridyl)phenyl?), [Pt(CNN)Cl] ( 2 ; CNN=6‐phenyl‐2,2′‐bipyridyl?), [Pt(CNC)(CNPh)] ( 3 ; CNC=2,6‐diphenylpyridyl2?), [Pt(R‐CNN)Cl] ( 4 ; R‐CNN=3‐(6′‐(2′′‐naphthyl)‐2′‐pyridyl)isoquinolinyl?), and [Pt(R‐CNC)(CNPh)] ( 5 ; R‐CNC=2,6‐bis(2′‐naphthyl)pyridyl2?). By considering both the spin–orbit coupling (SOC) and the electronic structures of these complexes at their respective optimized singlet ground (S0) and first triplet ( ) excited states, we were able to rationalize the experimental findings that 1) 1 is a strong emitter while its isomer 2 is only weakly emissive in CH2Cl2 solution at room temperature; 2) although the cyclometalated ligand of 3 has a higher ligand‐field strength than that of 1 , 3 is nonemissive in CH2Cl2 solution at 298 K; and 3) extension of π conjugation at the lateral aryl rings of the cyclometalated ligands of 2 and 3 to give 4 and 5 , respectively, leads to increased emission quantum yields under the same conditions. We found that Jahn–Teller and pseudo‐Jahn–Teller effects are operative in complexes 2 and 3 , respectively, on going from the optimized S0 ground state to the optimized excited state, and thus lead to large excited‐state structural distortions and hence fast nonradiative decay. Furthermore, a strong‐field ligand may push the two different occupied d orbitals so far apart that the SOC effect is small and the radiative decay rate is slow. This work is an example of electronic‐structure‐driven tuning of the phosphorescence efficiency, and the DFT/TDDFT approach is demonstrated to be a versatile tool for the design of phosphorescent materials with target characteristics. 相似文献
10.
R. G. Cooks T. Ast B. Kralj V. Kramer D. Ž igon 《Journal of the American Society for Mass Spectrometry》1990,1(1):16-27
The distribution Pε of internal energies deposited in W(CO)6 +?. ions upon charge stripping (that is, electron detachment to yield the doubly charged ion in the course of a single kiloelec-tronvolt energy collision) was estimated by a thermochemical method from the measured relative abundances of the doubly charged fragment ions produced. The thermochemical information needed to estimate P/ge was obtained by measuring the threshold translational energy losses associated with charge stripping of the singly charged fragment ions, W(CO) n + (n = 0-5). The P(/ge) curve falls exponentially with increasing internal energy. The average energy transferred to W(CO)6 +? upon a 7.8-keV collision with O2 is 19 eV, yielding W(CO)6 2? ions with an average of 4 eV of internal energy. In its general appearance, the P(ε) distribution associated with charge stripping is similar to the curves obtained from simple collisional activation of either W(CO) 6 +?. or W(CO)6 2+? in kiloelectronvolt energy gaseous collisions. Given that charge stripping occurs by way of an electronic excitation process, this similarity in the energy deposition function is taken to indicate that electronic excitation is also the major mechanism for simple collisional activation in this system at zero scattering angle in the kiloelectronvolt energy regime. The internal energy distribution associated with a related charge-stripping process, charge inversion from the metal carbonyl anions to yield the corresponding cations, was also recorded. This reaction shows a large (~7 eV) average internal energy deposition with a distribution that indicates near-zero probability of formation of unexcited ions. These data are tentatively interpreted in terms of vibrationalelectron detachment. The internal energy distribution associated with an exothermic process, charge exchange [W(CO)6 2+? + O2 → W(CO) + 6?+O2 +?], was also characterized. Unexpectedly strong coupling of translational to internal energy is observed, and there is a large probability of depositing internal energies in excess of 10 eV, even though the exothermicity is only 3 eV. Finally, the internal energy distributions associated with the formation of doubly charged W(CO)6 2+? ions by electron ionization have been measured. Unlike the distribution for charge stripping, but like that for singly charged ions generated by electron impact, this distribution shows considerable structure, presumably due to Franck-Condon factors. 相似文献
11.
X-ray photoelectron spectra of metatungstate H2W12O6?40 and of reduced derivatives with 5, 12, and 24 electrons have been recorded. W(4f) signals are consistent with the presence of tetravalent tungsten in the reduced species. In particular the 12e? derivative does not contain WV but WIV and WVI in equal amounts. Valence band spectra show the W(5d) levels near 2 eV in reduced forms, this energy being appreciably lower than in W bronzes and WO2. This can be correlated with the relative inertness of reduced metatungstates towards oxidation. 相似文献
12.
《Journal of organometallic chemistry》1986,311(3):C47-C50
Ring-closure via olefin coordination in coordinatively-unsaturated cis-[(η1-pdpp)W(CO)4], (pdpp = CH2CH(CH2)3P(C6H5)2, 4-pentenyldiphenylphosphine) produced via pulsed laser flash photolysis of cis-(pip)(η1-pdpp)W(CO)4 (pip = piperidine) in chlorobenzene has been identified unequivocally. Rates and activation parameters for this pathway and for competitive bimolecular interaction of pip at the solvated coordination site have been measured. 相似文献
13.
In the presence of Bu4NBr acting as phasetransfer reagent, organothiophosphoryl polyoxotungstate derivatives α-[RP(S)]2PW9O54^5- (R=C6Hs, C6H11) have been obtained by reaction of the trivacant β-[PW9O34]^9- anions with electrophilic C6H5P(S)Cl2 or C6H11P(S)Cl2 in acetonitrile. These new organic-inorganic hybrid anions have been characterized by elemental analysis, IR, ^31P and ^183W NMR spectroscopy. The collective application of the spectroscopy data of these new species indicates that the hybrid anion consists of an α-[PW9O34] framework on which are grafted two RP(S) groups through P-O-W bridges. The five-line ^183W spectra indicate that the hybrid anions possess Cs symmetry in acetonitrile. 相似文献
14.
Lorenzo-Luis Pablo A. Gili Pedro Sánchez Agustín Rodriguez-Castellón Enrique Jiménez-Jiménez José Ruiz-Pérez Catalina Solans Xavier 《Transition Metal Chemistry》1999,24(6):686-692
Tungstotellurates of the organic imidazolium and 4-methyl-imidazolium cations have been prepared and characterized by X-ray diffraction and i.r. spectroscopy. The [TeW6O24]6– anion is formed by close packing of oxygen atoms with Te and W atoms in distorted octahedral voids. In both compounds the organic cations are involved in hydrogen bonds, to the [TeW6O24]6– anion in [H2imz]6[TeW6O24] · 2(Himz) (1) and to Te(OH)6 units in [4-H2-methyl-imz]6[TeW6O24] · Te(OH)6 (2). Solution studies of (1) and (2) by 1H-, 183W- and 125Te-n.m.r. have been carried out. Thermogravimetric (t.g.) and calorimetric (d.s.c.) analyses were performed for both compounds. 相似文献
15.
Charles P. Casey William D. Jones Stephen G. Harsy 《Journal of organometallic chemistry》1981,206(3):C38-C42
The reaction of (η5-C5H5)W(CO)2(NO), 6W, with P(CH3)3 proceeds rapidly at 25°C to give (η5-C5H5)W(CO)(NO)[P(CH3)3], 7W. The rate of formation of 7W was found to be 4.48 × 10?2M?1 [6W] [P(CH3)3] at 25.0°c in THF. In neat P(CH3)3 at ?23°C, 6W is converted to (η1-C5H5)W(CO)2(NO)[P(CH3)3]2, 8W. In dilute solution, 8W decomposes to initially give a 2:1 mixture of 6W and 7W. The mixture is then converted to 7W. The reaction of (η5-C5H5)Mo(CO)(NO), 6Mo, with P(CH3)3 is 6.1 times faster than that of the tungsten analog. 相似文献
16.
Reduction of W(CO)3(PMTA) (PMTA = 1,1,4,7,7-pentamethyldiethylenetriamine) by six equivalents of potassium metal in liquid ammonia provides an incompletely characterized highly reduced carbonyltungstate ion which reacts with several electrophiles to provide derivatives containing only tungsten tricarbonyl units. These include W(CO)3(NH3)3, [W3(CO)9(μ-OC2H5)(μ3-OC2H5)2]3-, HW(CO)3(SnPh3)32- and the unusual [(Ph3Sn)2{(Ph2Sn)2OEt}W(CO)3]?. The latter compound results from an unprecedented phenyl-tin cleavage in the reaction of triphenyltin chloride and the highly reduced carbonyltungstate ion. Triphenyltin derivatives of the unknown M(CO)36- (M = Cr, Mo and W) have also been prepared by reacting M(CO)3(SnPh3)33- with Brønsted acids and Ph3SnCl. From these reactions the previously unknown HM(CO)3(SnPh3)32- (M = Cr, Mo and W) and M(CO)3(Ph3Sn)42- (M = Mo and W) have been isolated and characterized. The latter are the first compounds containing more than three triphenyltin units attached to one transition metal. 相似文献
17.
Vapour pressure measurements have been carried out on the complexes W(CO)it6-x (NCCH3x(x=1,2,3) and Mo(CO)it6-x(NCCH3x(x=1,3) employing the Knudsen effusion technique. The following enthalpies of sublimation, ΔH298sub(kJ mole?1), have been determined from vapour pressure data: W(CO)5(NCCH3)=98.1±2.0; W(CO) 4 (NCCH3)2=131.0±6.0; W(CO)3(NCCH33=103.4±6.0; Mo(CO)5(NCCH3)=105.8± 5.6; and Mo(CO)3(NCCH3)3=111.3±3.0. 相似文献
18.
《Journal of Coordination Chemistry》2012,65(9):785-790
Treatment of M(CO)6 (M?=?Cr, W) with (Ph2PMe2Si)3CH in toluene at elevated temperatures resulted in the isolation of pale green [Cr(CO)3{(Ph2PMe2Si)3CH}] and pale brown [W(CO)3{(Ph2PMe2Si)3CH}] in high yield. These complexes have been characterized by elemental analysis, conductivity measurements, TGA, mass spectrometry, and IR, electronic, 1H and 31P{1H} NMR spectroscopy. The complexes have pseudo octahedral geometry around the metal atom with tridentate coordination of the multidentate ligand. The six-membered MPSiCSiP metallacycles are shown to have high fluxionality at room temperature on the NMR time scale. 相似文献
19.
Prof. Dr. Takako Muraoka Ryosuke Ishizeki Shun Tanabe Dr. Keiji Ueno 《欧洲无机化学杂志》2023,26(18):e202300124
Silanethione compounds, R2Si=S, have been recognized as highly reactive species. One reliable way to stabilize silanethione is its coordination to transition metal fragments to convert silanethione-coordinated transition metal complexes. Herein, we report the synthesis, structure, and reactivity of a second cationic silanethione tungsten complex [Cp*(OC)3W{S=SiR2(py)}]TFPB (R=Me ( 5 a ), Ph ( 5 b ), Cp*: η5-C5Me5, py: pyridine, and TFPB−: [B{3,5-(CF3)2C6H3}4]−). Complex 5 was obtained by H− abstraction from the Si atom in the corresponding silylsulfanyl complex Cp*(OC)3W(SSiR2H) ( 4 ) with Ph3CTFPB, followed by the addition of pyridine. The reaction of 5 with PhNCS and PMe3 produced [Cp*(OC)3W{SSiR2N(Ph)C(PMe3)2}]TFPB (R=Me ( 6 a ), Ph ( 6 b )) via the elimination of pyridine and the addition of the 1,3-dipolar species PhNC(PMe3)2 ( A ) to the Si atom. 相似文献
20.
Prof. Dr. Wolfram W. Seidel Woldemar Dachtler Julia Semmler Marco Tänzler Manuel Folk Dr. Alexander Villinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14702-14711
A series of heterodinuclear complexes with acetylene dithiolate (acdt2?) as the bridging moiety were synthesised by a facile one‐pot procedure that avoided use of the highly elusive acetylene dithiol. Generation of the W–Ru complex [Tp′W(CN)(CO)(C2S2)Ru(η5‐C5H5)(PPh3)] (Tp’=hydrotris(3,5‐dimethylpyrazolyl)borate) and the W–Pd complexes [Tp′W(CN)(CO)(C2S2)Pd(dppe)] and [Tp′W(CO)2(C2S2)Pd(dppe)][PF6] (dppe=1,2‐bis(diphenylphoshino)ethane), which exhibit a [W(η2‐κ2‐C2S2)M] core (M=Ru, Pd), was accomplished by using a transition‐metal‐assisted solvolytical removal of the Me3Si‐ethyl thiol protecting groups. All intermediate species of the reaction have been fully characterised. The highly coloured W–Ru complex [Tp′W(CN)(CO)(C2S2)Ru(η5‐C5H5)(PPh3)] shows reversible redox chemistry, as does the prototype complex [Tp′W(CO)2(C2S2)Ru(η5‐C5H5)(PPh3)][PF6]. Single crystal X‐ray diffraction and IR, EPR and UV/Vis spectroscopic studies in conjunction with DFT calculations prove the high electronic delocalisation of states over the acdt2? linker. Comparative studies revealed a higher donor strength and more pronounced dithiolate character of acdt2? in [Tp′W(CN)(CO)(C2S2)Ru(η5‐C5H5)(PPh3)] relative to [Tp′W(CO)2(C2S2)Ru(η5‐C5H5)(PPh3)]+. In addition, the influence of the overall complex charge on the metric parameters was investigated by single‐crystal X‐ray diffraction studies with the W–Pd complexes [Tp′WL2(C2S2)Pd(dppe)] (L=(CN?)(CO) or (CO)2). The central [W(C2S2)Pd] units exhibit high structural similarity, which indicates the extensive delocalisation of charge over both metals. 相似文献