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1.
Alkali‐Metal Pyrazolate Complexes with Unusual Pyrazolate Coordination Modes and Pseudocubane Motifs
Samar Beaini Glen B. Deacon Prof. Dr. Anja P. Erven Dr. Peter C. Junk Prof. Dr. David R. Turner Dr. 《化学:亚洲杂志》2007,2(4):539-550
The dimeric complex [Li(Ph2pz)(OEt2)]2 ( 1 ) and tetrameric cluster [Na(Ph2pz)(thf)]4 ( 2 ) were prepared by treatment of alkali‐metal reagents (nBuLi and Na{N(SiMe3)2}, respectively) with 3,5‐diphenylpyrazole (Ph2pzH) in Et2O ( 1 ) or THF ( 2 ). The polymer [Na(tBu2pz)]n ( 3 ) was obtained from reaction at elevated temperature in a sealed tube between Na metal and 3,5‐di‐tert‐butylpyrazole (tBu2pzH). The complex [Na4(tBu2pz)2(thf)3(obds)]2 ( 4 ; obds=(OSiMe2)2O) was obtained as a minor product from prolonged treatment of tBu2pzH with elemental sodium in a silicone‐greased flask. All four alkali‐metal pyrazolato complexes were characterized by IR and 1H NMR spectroscopy and X‐ray crystallography.The Li dimer 1 displays μ‐η2:η1 lithium–pyrazolato binding, in which both lithium atoms are four‐coordinate. Room‐ and variable‐temperature NMR studies (1H, 13C, and 7Li) of 1 suggest similar behavior in solution, with peaks coalescing at low temperatures. Complexes 2 and 4 display distorted cubane structures. In 2 , all the sodium atoms are five‐coordinate, whereas 4 contains two sodium/pyrazolate/thf clusters (4:2:3 ratio) bridged by two obds2? units, as well as two four‐coordinate and two five‐coordinate sodium atoms. Compound 3 is composed of two independent chains with the unusual coordination modes μ3‐η5:η2:η2, μ3‐η5:η2:η1, and μ3‐η4:η2:η1, with five‐, six‐, and seven‐coordinate sodium atoms. Two oxo‐centered M8 cage complexes [(tBu2pz)6Li8O] ( 5 ) and [(tBu2pz)6Na8O] ( 6 ) were obtained as by‐products from attempted preparation of [Li(tBu2pz)] and [Na(tBu2pz)], respectively, and their structures were determined. 相似文献
2.
Dr. Zhifang Guo Dr. Victoria L. Blair Prof. Glen B. Deacon Prof. Peter C. Junk 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(3):e202103865
Unique outcomes have emerged from the redox transmetallation/ protolysis (RTP) reactions of europium metal with [Ag(C6F5)(py)] (py=pyridine) and pyrazoles (RR′pzH). In pyridine, a solvent not normally used for RTP reactions, the products were mainly EuII complexes, [Eu(RR′pz)2(py)4] (RR′pz=3,5-diphenylpyrazolate (Ph2pz) 1 ; 3-(2-thienyl)-5-trifluoromethylpyrazolate (ttfpz) 2 ; 3-methyl-5-phenylpyrazolate (PhMepz) 3 ). However, use of 3,5-di-tert-butylpyrazole (tBu2pzH) gave trivalent [Eu(tBu2pz)3(py)2] 4 , whereas the bulkier N,N′-bis(2,6-difluorophenyl)formamidine (DFFormH) gave divalent [Eu(DFForm)2(py)3] 5 . In tetrahydrofuran (thf), the usual solvent for RTP reactions, C−F activation was observed for the first time with [Ag(C6F5)(py)] in such reactions. Thus trivalent [{Eu2(Ph2pz)4(py)4(thf)2(μ-F)2}{Eu2(Ph2pz)4(py)2(thf)4(μ-F)2}] ( 6 ), [Eu2(ttfpz)4(py)2(dme)2(μ-F)2] ( 7 ), [Eu2(tBu2pz)4(dme)2(μ-F)2] ( 8 ) were obtained from the appropriate pyrazoles, the last two after crystallization from 1,2-dimethoxyethane (dme). Surprisingly 3,5-dimethylpyrazole (Me2pzH) gave the divalent cage [Eu6(Me2pz)10(thf)6(μ-F)2] ( 9 ). This has a compact ovoid core held together by bridging fluoride, thf, and pyrazolate ligands, the last including the rare μ4-1η5(N2C3): 2η2(N,N′): 3κ(N): 4κ(N′) pyrazolate binding mode. With the bulky N,N′-bis(2,6-diisopropylphenyl)formamidine (DippFormH), which often favours C−F activation in RTP reactions, neither oxidation to EuIII nor C−F activation was observed and [Eu(DippForm)2(thf)2] ( 10 ) was isolated. By contrast, Eu reacted with Bi(C6F5)3 and Ph2pzH or tBu2pzH in thf without C−F activation, to give [Eu(Ph2pz)2(thf)4] ( 11 ) and [Eu(tBu2pz)3(thf)2] ( 12 ) respectively, the oxidation state outcomes corresponding to that for use of [Ag(C6F5)(py)] in pyridine. 相似文献
3.
Samar Beaini Glen B. Deacon Craig M. Forsyth Peter C. Junk Prof. 《无机化学与普通化学杂志》2008,634(15):2903-2906
The complex [Yb(Ph2pz)3(LiOBu)]2 ( 1 ) (Ph2pz = 3,5‐diphenylpyrazolate), fortuitously obtained from reaction of Yb metal with a lithium containing sample of [SnMe3(Ph2pz)] at elevated temperatures forms a centrosymmetric butoxy‐ and pyrazolate‐bridged open box structure. Each ytterbium atom is eight coordinate with one chelating Ph2pz ligand, one μ‐η2:η2 bridging pyrazolate, one μ‐η2(Yb):η4(Li) Ph2pz group and two bridging butoxide ligands. Each lithium atom is unsymmetrically chelated by an η2‐Ph2pz group, η4(N,C(pz)C2(Ph)) bonded by another pyazolate group, and bridged through a butoxide oxygen atom to two ytterbium atoms. The type of η4‐pyrazolate coordination is unprecedented and is the first observation of interactions to a metal by the Ph rings of the Ph2pz ligand. The complex [Li(dme)3][Eu(Ph2pz)3(dme)] ( 2 ) obtained from reaction of Eu metal with the same sample of [SnMe3(Ph2pz)] in dme at room temperature is a charged separated species with the first anionic pyrazolatolanthanoidate(II) complex in which europium is eight coordinate with three chelating Ph2pz ligands and a chelating dme. 相似文献
4.
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes XXI The Influence of the PR3 Ligands on Formation and Properties of the Phosphinophosphinidene Complexes [{η2‐tBu2P–P}Pt(PR3)2] and [{η2‐tBu2P1–P2}Pt(P3R3)(P4R′3)] (R3P)2PtCl2 and C2H4 yield the compounds [{η2‐C2H4}Pt(PR3)2] (PR3 = PMe3, PEt3, PPhEt2, PPh2Et, PPh2Me, PPh2iPr, PPh2tBu and P(p‐Tol)3); which react with tBu2P–P=PMetBu2 to give the phosphinophosphinidene complexes [{η2‐tBu2P–P}Pt(PMe3)2], [{η2‐tBu2P–P}Pt(PEt3)2], [{η2‐tBu2P–P}Pt(PPhEt2)2], [{η2‐tBu2P–P}Pt(PPh2Et)2], [{η2‐tBu2P–P}Pt(PPh2Me)2], [{η2‐tBu2P–P}Pt(PPh2iPr], [{η2‐tBu2P–P}Pt(PPh2tBu)2] and [{η2‐tBu2P–P}Pt(P(p‐Tol)3)2]. [{η2‐tBu2P–P}Pt(PPh3)2] reacts with PMe3 and PEt3 as well as with tBu2PMe, PiPr3 and P(c‐Hex)3 by substituting one PPh3 ligand to give [{η2‐tBu2P1–P2}Pt(P3Me3)(P4Ph3)], [{η2‐tBu2P1–P2}Pt(P3Ph3)(P4Me3)], [{η2‐tBu2P1–P2}Pt(P3Et3)(P4Ph3)], [{η2‐tBu2P1–P2}Pt(P3MetBu2)(P4Ph3)], [{η2‐tBu2P1–P2}Pt(P3iPr3)(P4Ph3)] and [{η2‐tBu2P1–P2}Pt(P3(c‐Hex)3)(P4Ph3)]. With tBu2PMe, [{η2‐tBu2P–P}Pt(P(p‐Tol)3)2] forms [{η2‐tBu2P1–P2}Pt(P3MetBu2)(P4(p‐Tol)3)]. The NMR data of the compounds are given and discussed with respect to the influence of the PR3 ligands. 相似文献
5.
Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐ray Crystal Structures of [Ru2(CO)n(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (n = 4; 5) and [Ru2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] The reaction of [Ru2(μ‐CO)(CO)5(μ‐H)(μ‐PtBu2)(tBu2PH)] ( 2 ) with dppm yields the dinuclear species [Ru2(μ‐CO)(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 3 ) (dppm = Ph2PCH2PPh2). Under thermal or photolytic conditions 3 loses very easily one carbonyl ligand and affords the corresponding electronically and coordinatively unsaturated complex [Ru2(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 4 ). 4 is also obtainable by an one‐pot synthesis from [Ru3(CO)12], an excess of tBu2PH and stoichiometric amounts of dppm via the formation of [Ru2(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)2] ( 1 ). 4 exhibits a Ru–Ru double bond which could be confirmed by addition of methylene to the dimetallacyclopropane [Ru2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 5 ). The molecular structures of 3 , 4 and 5 were determined by X‐ray crystal structure analyses. 相似文献
6.
Thorsten Morawitz Michael Bolte Hans‐Wolfram Lerner Matthias Wagner 《无机化学与普通化学杂志》2008,634(9):1570-1574
The synthesis and full characterization of the sterically demanding ditopic lithium bis(pyrazol‐1‐yl)borates Li2[p‐C6H4(B(Ph)pzR2)2] is reported (pzR = 3‐phenylpyrazol‐1‐yl ( 3 Ph), 3‐t‐butylpyrazol‐1‐yl ( 3 tBu)). Compound 3 Ph crystallizes from THF as THF‐adduct 3 Ph(THF)4 which features a straight conformation with a long Li···Li distance of 12.68(1) Å. Compound 3 tBu was found to function as efficient and selective scavenger of chloride ions. In the presence of LiCl it forms anionic complexes [ 3 tBuCl]− with a central Li‐Cl‐Li core (Li···Li = 3.75(1) Å). 相似文献
7.
Hans‐Christian Bttcher Marion Graf Kurt Merzweiler Christoph Wagner 《无机化学与普通化学杂志》2001,627(5):903-908
Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)], and [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)] [Ru3Rh(CO)7(μ3‐H)(μ‐PtBu2)2(tBu2PH)(μ‐Cl)2] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) Å3. The reaction of 4 with dppm (Ph2PCH2PPh2) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 Å3. Moreover single crystals of [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P21/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) Å3. 相似文献
8.
Coordinatively Unsaturated Diiron Complexes: Synthesis and Crystal Structures of [Fe2(CO)4(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] and [Fe2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] [Fe2(μ‐CO)(CO)6(μ‐H)(μ‐PtBu2)] ( 1 ) reacts spontaneously with dppm (dppm = Ph2PCH2PPh2) to give [Fe2(μ‐CO)(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 2 c ). By thermolysis or photolysis, 2 c loses very easily one carbonyl ligand and yields the corresponding electronically and coordinatively unsaturated complex [Fe2(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 3 ). 3 exhibits a Fe–Fe double bond which could be confirmed by the addition of methylene to the corresponding dimetallacyclopropane [Fe2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 4 ). The reaction of 1 with dppe (Ph2PC2H4PPh2) affords [Fe2(μ‐CO)(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppe)] ( 5 ). In contrast to the thermolysis of 2 c , yielding 3 , the heating of 5 in toluene leads rapidly to complete decomposition. The reaction of 1 with PPh3 yields [Fe2(CO)6(H)(μ‐PtBu2)(PPh3)] ( 6 a ), while with tBu2PH the compound [Fe2(μ‐CO)(CO)5(μ‐H)(μ‐PtBu2)(tBu2PH)] ( 6 b ) is formed. The thermolysis of 6 b affords [Fe2(CO)5(μ‐PtBu2)2] and the degradation products [Fe(CO)3(tBu2PH)2] and [Fe(CO)4(tBu2PH)]. The molecular structures of 3 , 4 and 6 b were determined by X‐ray crystal structure analyses. 相似文献
9.
Ansa‐Complexes of [Mn(η5‐C5H5)(η6‐C6H6)]: Preparation,Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3) 下载免费PDF全文
Prof. Dr. Holger Braunschweig Dr. Alexander Damme Dr. Klaus Dück Dr. Marco Fuß Dr. Christian Hörl Dr. Thomas Kramer Dr. Ivo Krummenacher Dr. Thomas Kupfer Valerie Paprocki Christoph Schneider 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14797-14803
We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa‐bridging elements. Their preparation was achieved by salt‐elimination reactions of the dilithiated precursor [Mn(η5‐C5H4Li)(η6‐C6H5Li)]?pmdta (pmdta=N,N,N′,N′,N′′‐pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single‐atom‐bridged derivatives, [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] and [Mn(η5‐C5H4)(η6‐C6H5)SiPh2], could also be determined by X‐ray structural analysis. We investigated for the first time the reactivity of these ansa‐cyclopentadienyl–benzene manganese compounds. The reaction of the distannyl‐bridged complex [Mn(η5‐C5H4)(η6‐C6H5)Sn2tBu4] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn?Sn bond to give a triatomic ansa‐bridge. The investigation of the ring‐opening polymerization (ROP) capability of [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] with [Pt(PEt3)3] showed that an unexpected, unselective insertion into the Cipso?Sn bonds of [Mn(η5‐C5H4)(η6‐C6H5)SntBu2] had occurred. 相似文献
10.
Hans‐Christian Bttcher Marion Graf Kurt Merzweiler Christoph Wagner 《无机化学与普通化学杂志》2000,626(2):597-603
Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐Ray Crystal Structures of [Ru2(CO)4(μ‐H)(μ‐S)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)], [Ru2(CO)4(μ‐X)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (X = Cl, S2CH) [Ru2(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 1 ) reacts in benzene with elemental sulfur to the addition product [Ru2(CO)4(μ‐H)(μ‐S)(μ‐PtBu2)(μ‐dppm)] ( 2 ) (dppm = Ph2PCH2PPh2). 2 is also obtained by reaction of 1 with ethylene sulfide. The reaction of 1 with carbon disulfide yields with insertion of the CS2 into the Ru2(μ‐H) bridge the dithioformato complex [Ru2(CO)4(μ‐S2CH)(μ‐PtBu2)(μ‐dppm)] ( 3 ). Furthermore, 1 reacts with [NO][BF4] to the complex salt [Ru2(CO)4(μ‐NO)(μ‐H)(μ‐PtBu2)(μ‐dppm)][BF4] ( 4 ), and reaction of 1 with CCl4 or CHCl3 affords spontaneously [Ru2(CO)4(μ‐Cl)(μ‐PtBu2)(μ‐dppm)] ( 5 ) in nearly quantitative yield. The molecular structures of 2 , 3 and 5 were confirmed by crystal structure analyses. 相似文献
11.
The Syntheses,Structures, and Magnetic Properties of Four 2D Lanthanide(III)‐naphthalenedicarboxylic Complexes 下载免费PDF全文
Ying‐Bing Lu Lei‐Peng Chen Shi‐Yong Zhang Ping Lian Yong‐Rong Xie 《无机化学与普通化学杂志》2015,641(14):2408-2413
Four Ln‐NDC coordination polymers [Ln(NDC)(HNDC)(H2O)] (Ln = La ( 1 ), Pr ( 2 ), Nd ( 3 ), Sm ( 4 ), H2NDC = 1,4‐naphthalenedicarboxylic acid) were hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, and single‐crystal X‐ray diffraction. Compounds 1 – 4 are isomorphous, and their structures display a layer constructed from a Ln‐organic chain and NDC2– ligand, in which the H2NDC ligands adopt two different acidity‐dependent types and coordination modes: HNDC1– with μ‐η1:η1 and NDC2– with μ‐η1:η2:η1:η2. The 3D supramolecular networks of 1 – 4 are mainly controlled by hydrogen bonds interactions. The magnetic susceptibilities of complexes 2 – 4 reveal overall antiferromagnetic interactions between the LnIII ions. In addition, thermogravimetric analysis of compound 2 is described. 相似文献
12.
Reaction of [Ru(η6‐p‐cymene)Cl2]2 with two equivalents of [Ph4P][Cl] in CH2Cl2 yields [Ph4P][Ru(η6‐p‐cymene)Cl3], containing a trichlororuthenate(II) anion. In solution, an equilibrium between the product and [Ru(η6‐p‐cymene)Cl2]2 is observed, which in CDCl3 is nearly completely shifted to the dimer, whereas in CD2Cl2 essentially a 1:1‐mixture of the two ruthenium species is present. Crystallization from CH2Cl2/pentane yielded two different crystals, which were identified by X‐ray analysis as [Ph4P][Ru(η6‐p‐cymene)Cl3] and [Ph4P][Ru(η6‐p‐cymene)Cl3]·CH2Cl2. 相似文献
13.
Reactions of the oxorhenium(V) complexes [ReOX3(PPh3)2] (X = Cl, Br) with the N‐heterocyclic carbene (NHC) 1,3,4‐triphenyl‐1,2,4‐triazol‐5‐ylidene (LPh) under mild conditions and in the presence of MeOH or water give [ReOX2(Y)(PPh3)(LPh)] complexes (X = Cl, Br; Y = OMe, OH). Attempted reactions of the carbene precursor 5‐methoxy‐1,3,4‐triphenyl‐4,5‐dihydro‐1H‐1,2,4‐triazole ( 1 ) with [ReOCl3(PPh3)2] or [NBu4][ReOCl4] in boiling xylene resulted in protonation of the intermediately formed carbene and decomposition products such as [HLPh][ReOCl4(OPPh3)], [HLPh][ReOCl4(OH2)] or [HLPh][ReO4] were isolated. The neutral [ReOX2(Y)(PPh3)(HLPh)] complexes are purple, airstable solids. The bulky NHC ligands coordinate monodentate and in cis‐position to PPh3. The relatively long Re–C bond lengths of approximate 2.1Å indicate metal‐carbon single bonds. 相似文献
14.
M. Rohrmüller S. Herres‐Pawlis M. Witte W. G. Schmidt 《Journal of computational chemistry》2013,34(12):1035-1045
Based on the equilibrium geometries of [Cu2(dbdmed)2O2]2+ and [Cu2(en)2O2]2+ obtained within density‐functional theory, we investigate their molecular electronic structure and optical response. Thereby results from occupation‐constrained as well as time‐dependent DFT (ΔSCF and TDDFT) are compared with Green's function‐based approaches within many‐body perturbation theory such as the GW approximation (GWA) to the quasiparticle energies and the Bethe‐Salpeter equation (BSE) approach to the optical absorption. Concerning the ground‐state energies and geometries, no clear trend with respect to the amount of exact exchange in the DFT calculations is found, and a strong dependence on the basis sets is to be noted. They affect the energy difference between bis‐μ‐oxo and μ‐η2:η2‐peroxo complexes by as much as 0.8 eV (18 kcal/mol). Even stronger, up to 5 eV is the influence of the exchange‐correlation functional on the gap values obtained from the Kohn‐Sham eigenvalues. Not only the value itself but also the trends observed upon the bis‐μ‐oxo to μ‐η2:η2‐peroxo transition are affected. In contrast, excitation energies obtained from ΔSCF and TDDFT are comparatively robust with respect to the details of the calculations. Noteworthy, in particular, is the near quantitative agreement between TDDFT and GWA+BSE for the optical spectra of [Cu2(en)2O2]2+. © 2013 Wiley Periodicals, Inc. 相似文献
15.
Prof. Dr. Holger Braunschweig Alexander Damme Dr. Daniela Gamon Hauke Kelch Dr. Ivo Krummenacher Dr. Thomas Kupfer Dr. Krzysztof Radacki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(27):8430-8436
We describe the synthesis of base‐free bisborole [Cym?(BC4Ph4)2]—Cym?=(OC)3Mn(η5‐C5H3)—and its transformation into two fully characterized Lewis acid–base adducts with pyridine bases of the type 4‐R? NC5H4 (R=tBu, NMe2). The results of electrochemical, as well as NMR and UV/Vis spectroscopic studies on [Cym?(BC4Ph4)2] and the related monoborole derivative [Cym(BC4Ph4)]—Cym=(OC)3Mn(η5‐C5H4)—provided conclusive evidence for 1) the enhanced Lewis acidity of the two boron centers that result from conjugation of two borole fragments, and 2) the fact that Mn? B bonding interactions between the Lewis acidic borole moieties and the Mn center are considerably less pronounced for bisborole [Cym?(BC4Ph4)2]. In addition, the reduction chemistry of [Cym?(BC4Ph4)2] has been studied in detail, both electrochemically and chemically. Accordingly, chemical reduction of [Cym?(BC4Ph4)2] with magnesium anthracene afforded the corresponding tetraanion, which features a rare Mg? OC bonding mode in the solid state. 相似文献
16.
[Fe2(μsb‐CO)(CO)3(NO)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]: Synthesis, X‐ray Crystal Structure and Isomerization Na[Fe2(μ‐CO)(CO)6(μ‐PtBu2)] ( 1 ) reacts with [NO][BF4] at —60 °C in THF to the nitrosyl complex [Fe2(CO)6(NO)(μ‐PtBu2)] ( 2 ). The subsequent reaction of 2 with phosphanes (L) under mild conditions affords the complexes [Fe2(CO)5(NO)L(μ‐PtBu2)], L = PPh3, ( 3a ); η‐dppm (dppm = Ph2PCH2PPh2), ( 3b ). In this case the phosphane substitutes one carbonyl ligand at the iron tetracarbonyl fragment in 2 , which was confirmed by the X‐ray crystal structure analysis of 3a . In solution 3b loses one CO ligand very easily to give dppm as bridging ligand on the Fe‐Fe bond. The thus formed compound [Fe2(CO)4(NO)(μ‐PtBu2)(μ‐dppm)] ( 4 ) occurs in solution in different solvents and over a wide temperature range as a mixture of the two isomers [Fe2(μsb‐CO)(CO)3(NO)(μ‐PtBu2)(μ‐dppm)] ( 4a ) and [Fe2(CO)4(μ‐NO)(μ‐PtBu2)(μ‐dppm)] ( 4b ). 4a was unambiguously characterized by single‐crystal X‐ray structure analysis while 4b was confirmed both by NMR investigations in solution as well as by means of DFT calculations. Furthermore, the spontaneous reaction of [Fe2(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 5 ) with NO at —60 °C in toluene yields a complicated mixture of products containing [Fe2(μ‐CO)(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 6 ) as main product beside the isomers 4a and 4b occuring in very low yields. 相似文献
17.
M. N. Sokolov N. E. Fedorova N. V. Pervukhina E. V. Peresypkina A. V. Virovets R. Pätow V. E. Fedorov D. Fenske 《Russian Chemical Bulletin》2006,55(1):53-61
Mono-and dinuclear ReIV and ReV complexes with 3,5-dimethylpyrazole (Me2pzH) were synthesized. The cis-[Re2O3Cl4(3,5-Me2pzH)4] complex (cis-1) was prepared by the reaction of NH4ReO4 with K[HB(Me2pz)3] in concentrated HCl or by refluxing of [ReCl3(MeCN)(PPh3)2] with Me2pzH in air. The bromide complex trans-[Re2O3Br4(3,5-Me2pzH)4] (trans-2) was synthesized by passing dry HBr through a solution of [Re2O3Br2(μ-3,5-Me2pz)2(3,5-Me2pzH)2] (4) in chloroform. The pyrazolate-bridged complex [Re2O3Cl2(μ-3,5-Me2pz)2(3,5-Me2pzH)2] (3) was prepared from (Et4N)2[ReOCl5] or Cs2[ReOCl5] and Me2pzH. The corresponding bromide and iodide complexes [Re2O3X2(3,5-Me2pz)2(3,5-Me2pzH)2] · C6H6 (X = Br (4) or I (5)) were synthesized by the reactions of (NH4)2[ReBr6] or K2[ReI6], respectively, with Me2pzH. The [ReO(OMe)(3,5-Me2pzH)4]Br2 · · 3,5-Me2pzH · 4H2O complex (6) was obtained as a by-product in the synthesis of complex 4. The reaction of [ReNCl2(PPh3)2] with Me2pzH was accompanied by hydrolytic denitration giving rise to the mixed-ligand complex [Re2O3Cl2(μ-3,5-Me2pz)2(3,5-Me2pzH)(PPh3)] (7). The reaction of (NH4)2[ReBr6] with a Me2pzH melt gave the trans-[ReBr4(3,5-Me2pzH)2] · · Me2CO complex (8). The structures of complexes 2 and 4–8 were established by X-ray diffraction. All compounds were characterized by elemental analysis, electronic absorption spectroscopy,
1H NMR and IR spectroscopy, mass spectrometry, and cyclic voltammetry.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 52–59, January, 2006. 相似文献
18.
Antoni Konitz Harald Krautscheid Jerzy Pikies 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(1):m21-m23
The crystal structure of the title compound, [Pt(C8H18P2)(C9H21P)(C18H15P)] or [(Ph3P)(tBu2PMe)Pt(η2‐tBu2PP)], contains four molecules in the asymmetric unit with slightly different conformations. The P—P distances in the tBu2PP ligands are similar for all four molecules [2.0661 (13)–2.0678 (13) Å] and indicate a multiple character of the P—P bond in the tBu2PP ligand. Molecules of the asymmetric unit can be assembled into a tetrahedron that fulfils the requirements for a rhombic disphenoid. The coordination of the Pt atom in all four molecules is square planar, with r.m.s. deviations from the PtP4 planes in the range 0.03–0.05 Å. All planes of the PtP4 groups are approximately parallel to the ab plane of the unit cell. The structure represents an unusual unsymmetrical platinum phosphinidene derivative. 相似文献
19.
Harald Krautscheid Eberhard Matern Jolanta Olkowska‐Oetzel Jerzy Pikies Gerhard Fritz 《无机化学与普通化学杂志》2001,627(7):1505-1507
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXIV. Formation and Structure of [μ‐(1,2 : 2‐η‐tBu2P–P){Mo(CO)2cp′}2] [cp′Mo(CO)2]2 (cp′ = C5H4tBu) reacts with tBu2P–P=P(Me)tBu2 to yield the compound [μ‐(1,2 : 2‐η‐tBu2P–P){Mo(CO)2cp′}2], which crystallizes in the space group P212121 with a = 1202.42(7), b = 1552.48(8), and c = 1765.3(1) pm. 相似文献
20.
Dinuclear Rare‐Earth Metal Alkyl Complexes Supported by Indolyl Ligands in μ‐η2:η1:η1 Hapticities and their High Catalytic Activity for Isoprene 1,4‐cis‐Polymerization 下载免费PDF全文
Guangchao Zhang Yun Wei Liping Guo Prof. Dr. Xiancui Zhu Prof. Dr. Shaowu Wang Prof. Dr. Shuangliu Zhou Xiaolong Mu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2519-2526
Two series of new dinuclear rare‐earth metal alkyl complexes supported by indolyl ligands in novel μ‐η2:η1:η1 hapticities are synthesized and characterized. Treatment of [RE(CH2SiMe3)3(thf)2] with 1 equivalent of 3‐(tBuN?CH)C8H5NH ( L1 ) in THF gives the dinuclear rare‐earth metal alkyl complexes trans‐[(μ‐η2:η1:η1‐3‐{tBuNCH(CH2SiMe3)}Ind)RE(thf)(CH2SiMe3)]2 (Ind=indolyl, RE=Y, Dy, or Yb) in good yields. In the process, the indole unit of L1 is deprotonated by the metal alkyl species and the imino C?N group is transferred to the amido group by alkyl CH2SiMe3 insertion, affording a new dianionic ligand that bridges two metal alkyl units in μ‐η2:η1:η1 bonding modes, forming the dinuclear rare‐earth metal alkyl complexes. When L1 is reduced to 3‐(tBuNHCH2)C8H5NH ( L2 ), the reaction of [Yb(CH2SiMe3)3(thf)2] with 1 equivalent of L2 in THF, interestingly, generated the trans‐[(μ‐η2:η1:η1‐3‐{tBuNCH2}Ind)Yb(thf)(CH2SiMe3)]2 (major) and cis‐[(μ‐η2:η1:η1‐3‐{tBuNCH2}Ind)Yb(thf)(CH2SiMe3)]2 (minor) complexes. The catalytic activities of these dinuclear rare‐earth metal alkyl complexes for isoprene polymerization were investigated; the yttrium and dysprosium complexes exhibited high catalytic activities and high regio‐ and stereoselectivities for isoprene 1,4‐cis‐polymerization. 相似文献