Magnesium acetate solvates, Mg(OAc)2 · nL, and their hydrates were prepared by crystallization of Mg(OAc)2 · 4H2O or Mg(OAc)2 from different solvents (L = MeOH, EtOH, HOAc). Anhydrous Mg(OAc)2 was obtained by thermal dehydration of the tetrahydrate at 150 °C. X‐ray single crystal diffraction mostly with the use of synchrotron radiation allowed the structure determination of Mg(OAc)2(H2O)3(EtOH) ( I ), Mg(OAc)2(HOAc)2(H2O)2 ( II ), Mg3(OAc)6(MeOH)6 ( III ), Mg3(OAc)6(HOAc)2(H2O)2 · 2HOAc ( IV ), Mg(OAc)2(HOAc) · 1.8(HOAc) ( V ), Mg(OAc)2 · H2O ( VI ), [Mg3(OAc)6(EtOH)2] · 2EtOH ( VII ), and Mg(OAc)2 ( VIII ). Structural data were discussed in terms of the number of neutral O‐donor ligands per magnesium atom, coordination environment of magnesium atoms, structural functions of acetate groups, and hydrogen bonding systems. 相似文献
Reaction of [Ru2(μ-CO)(CO)4{μ-(RO)2PN(Et)(OR)2}2] (R = Me or Pri) with the protonic acids HCl, HBr, HNO3, H2BO2F, CF3COOH, PhSH/HPF6, and H2CO3/HPF6 produces [Ru2A(CO)5 {μ-(RO)2PN(Et)(OR)2}2]+ and/or [Ru2(μ-A)(CO)4{μ-(RO)2PN(Et)(OR)2}2]+ (A = Cl, Br, ON(O)O, OB(F)OH, OC(CF3)O, SPh, and OC(OH)O) via [Ru2H(CO)5{μ-(RO)2PN(Et)(OR)2}2]+ as intermediate; the structure of [Ru2{μ-OB(F)OH}(CO)4{-(PriO)2PN(Et)P(OPri)2}]+ has been established X-ray crystallographically. 相似文献
The positive-ion mass spectra of the following organonitrogen derivatives of metal carbonyls are discussed: (i) The compounds NC5H4CH2Fe(CO)2C5H5, NC5H4CH2COMo(CO)2C5H5, NC5H4CH2W(CO)3C5H5, NC5H4CH2COMn(CO)4, C5H10NCH2CH2Fe(CO)2C5H5, (CH3)2NCH2CH2COFeCOC5H5 and (CH3)2NCH2CH2COMn(CO)4 obtained from metal carbonyl anions and haloalkylamines, (ii) The isocyanate derivative C5H5Mo(CO)3CH2NCO; (iii) The arylazomolybdenum derivatives RN2Mo(CO)2C5H5 (R ? phenyl, p-tolyl, or p-anisyl); (iv) The compound (C6H5N)2COFe2(CO)6 obtained from Fe3(CO)12 and phenyl isocyanate; (v) The N,N,N′,N′-tetramethylethylenediamine complex (CH3)2NCH2CH2N(CH3)2W(CO)4. Further examples of eliminations of hydrogen, CO, and C2H2 fragments were noted. In addition evidence for the following more unusual processes was obtained: (i) Elimination of HCN fragments from the ions [NC5H4CH2MC5H5]+ to give the ions [(C5H5)2M]+ (M ? Fe, Mo and W); (ii) Conversion of C5H5Mo(CO)3CH2NCO to C5H5Mo(CO)2CH2NCO within the mass spectrometer; (iii) Elimination of N2 from [RN2MoC5H5]+ to give [RMoC5H5]+; (iv) Novel eliminations of HNCO, FeNCO, and C6H5NC fragments in the mass spectrum of (C6H5N)2COFe2(CO)6; (v) Facile dehydrogenation of the N,N,N′,-N′-tetramethylethylenediamine ligand in the complex (CH3)2NCH2CH2N(CH3)2W(CO)4. 相似文献
The PH bond of dialkylphosphites (dimethylphosphite, 5,5-dimethyl-1,3-dioxa-2-phosphorinane and 4,4,5,5-tetramethyl-1,3-dioxa-2-phospholane) oxidatively adds to irClL2(L = PPh3, AsPh3) and IrCl(PMe2Ph)3 generated in situ to give six-coordinate hydrido(dialkylphosphonato)iridium(III) complexes, e.g. IrHClL2[{(MeO)2-PO}2H] and IrHCl(PMe2Ph)3[PO(OMe)2]. Addition of triphenylphosphine to a solution containing [IrCl(C8H14)2]2 and dimethylphosphite in a 1:2 mol ratio gives a five-coordinate hydrido (dimethylphosphonato)iridium(III) complex IrHCl(PPh3)2{PO(OMe)2}, from which six-coordinate pyridine and acetylacetonato complexes IrHCl(PPh3)2(C5H5N){PO(OMe)2} and IrH(PPh3)2(acac){PO(OMe)2} can be obtained. The ligand arrangements in the various complexes are inferred from IR, 1H and 31P NMR data. 相似文献
The synthesis and structures of mononuclear Ni(II), Co(II), Mn(II), and Cu(II) pivalates isolated as complex salts NBu4[M(Piv)3] ((NBu4)+ is tetrabutylammonium cation, Piv– is pivalate anion) and polynuclear complexes [Ni6(L)2(HL)2(Piv)6(HPiv)8], (NBu4)2[Co4(Piv)8(AcO)2(H2O)4], NBu4[Co2(Piv)5(H2O)2], and (NBu4)2[Cu4(Piv)8(AcO)2(H2O)2] (L2–, HL–, and AcO– is lactic acid dianion, lactic acid monoanion, and acetate anion, respectively) are discussed. The formation of the compounds is detected during the development of the synthesis of NBu4[M(Piv)3]. 相似文献
The new heterometallic complex {μ-1,3,5-[CH(pz)2]3C6H3}[Re(CO)3Br][Pt(p-tolyl)2]2 has been prepared by reaction of 1 equiv. of the dimer [Pt(p-tolyl)2(μ-SEt2)]2 with the monometallic rhenium precursor {1,3,5-[CH(pz)2]3C6H3}Re(CO)3Br, where 1,3,5-[CH(pz)2]3C6H3 is the tritopic, arene-linked bis(pyrazolyl)methane ligand 1,3,5-tris[bis(1-pyrazolyl)methyl]benzene. Similarly, the heterometallic complex {μ-1,3,5-[CH(pz)2]3C6H3}[Re(CO)3Br]2[Pt(p-tolyl)2] has been made by the reaction of the dirhenium compound {μ-1,3,5-[CH(pz)2]3C6H3}[Re(CO)3Br]2 and one-half of an equivalent of [Pt(p-tolyl)2(μ-SEt2)]2. X-ray crystallographic studies of the new compounds reveal significant noncovalent interactions in their molecular and supramolecular structures. 相似文献
The recent discovery of boronyl complexes of the type (R3P)2Pt(BO)X (R = cyclohexyl; X = halogen) makes of interest the chemistry of complexes of the related thioboronyl (BS) ligand. In this connection, the binuclear iron carbonyl complex Fe2(BS)2(CO)8 is predicted by density functional theory to have a symmetrical unbridged structure similar to the valence isoelectronic Mn2(CO)10. Higher-energy unsymmetrical (OC)5Fe → Fe(BS)2(CO)3 structures are also found as well as a doubly bridged Fe2(BS)2(CO)6(µ-CO)2 structure. The complex Fe2(BS)2(CO)8 is predicted to be viable toward symmetrical dissociation into Fe(BS)(CO)4 fragments. However, the unsymmetrical dissociation of Fe2(BS)2(CO)8 into Fe(CO)5 + Fe(BS)2(CO)3 is predicted to be exothermic by ~9 kcal mol?1. The low-energy structures of the mononuclear Fe(BS)2(CO)3 include structures in which the two BS ligands have coupled to form a B2S2 ligand through B–B bond formation. 相似文献
Metalluorene complexes (π-C5H5)M(CO)(C12H8) (IVa)-(IVc) and (π-C5H5) (CO)(C12F8) (IVd)-(IVf) (M = Co, Rh and Ir) have been prepared from reactions of the appropriate (π-cyclopentadienyl) carbonylmetal diiodides with 2,2′-dilithhiolbiphenyl (IIa) and 2,2′-dilithiooctafluorobiphenyl (IIb), respectively The triphenylphoshine substitution reactions of cobalt compounds (IVa) and (IVd) have also been studied. Reaction of (IIa) and (IIb) with norbornadieneplatinum dichloride result in the preparation of metallocyclic platinum compounds (π-C7H8) and (π-C7H8)Pt(C12H8). A reaction of (IIb) with zirconocene dichloride produces (π-C5H5)2Zr(C12F8), the first example of a ziconium-containing metalofluorene. 相似文献
Novel mixed complexes 2,4,6-Me3C6H2SZnS2CNEt2 (1), 2,4,6-Me3C6H2SeZnSe2CNEt2 (2) and their pyridine adducts ([Zn(SC6H2Me3-2,4,6)2(C5H5N)2] (3), [Zn(SeC6H2Me3-2,4,6)2(C5H5N)2] (4) and (Et2CNSe2)2Zn.NC5H5(5) and (Et2CNS2)2Zn.NC5H5(6) have been synthesised and characterised. The X-ray single crystal structures of (4), (5) and (6) have been determined. 相似文献
The activation of the CN triple bond of benzonitrile in the presence of acetic acid and of Os3(CO)12 or H2Os3(CO)10 has been studied. When Os3(CO)12 reacts with PhCN and acetic acid in refluxing n-octane the three main products are (μ-H)Os3(CO)10(μ-O2CCH3) (I), (μ-H)Os3(CO)10(μ-NCHPh) (II) and (μ-H)Os3(CO)10(μ-NHCH2Ph) (III); II and III are analogues of (μ-H)Ru3(CO)10(μ-NCHPh) and (μ-H)Ru3(CO)10(μ-NHCH2Ph) obtained from PhCN, Ru3(CO)12 or H4Ru4(CO)]12, and acetic acid. In contrast to the reaction with ruthenium clusters, Os3(CO)12 and H2Os3(CO)10 also give the adduct Os3(CO)10(CH3COOH) (I). The structure of I has been fully elucidated by X-ray diffraction. Crystals of I are monoclinic, space group P21/m, with unit cell parameters a 7.858(6), b 12.542(8), c 9.867(6) Å, β 109.92(2)°, Z = 2. In I an edge of the triangular cluster of osmium atoms is doubly bridged by a hydride and an acetate ligand. Ten terminal carbonyl groups are bonded to the metal atoms. 相似文献
The crosslinking of the acetylene-terminated monomer (1,4-HCCCH2-OC6H4)2CMe is catalyzed by (η-Cp)2Co, (η-Cp)Co(CO)2, (Ph3P)2MCl2 (M = Ni, Pd), (Ph3P)3RhCl and (η-Cp)2Ni (the last being highly active). Differential scanning calorimetry shows that the exotherm peak temperature is reduced. 相似文献
The reactions of Pt(PPH3)4 and Pt(C2H4)(PPh3)2 with CH2ClI have been investigated. The product of the reaction of Pt(PPh3)4 with CH2ClI is the cationic ylide complex cis-[Pt(CH2PPh3)Cl(PPh3)2][I], whereas the reaction of Pt(C2H4)-(PPh3)2 gives the oxidative addition product Pt(CH2Cl)I(PPh3)2. Reaction of cis- or trans-Pt(CH2Cl)I(PPh3)2] with PPh3 gives the complex cis-[Pt(CH2PPh3)-Cl(PPh3)2][I]. The structures of the complexes cis-[Pt(CH2PPh3X(PPh3)2][I] (where X = Cl or I) have been determined by X-ray crystallography. Both complexes crystalize in the monoclinic space group P21/n. For X = Cl a 1388.6(7), b 2026.7(10), c 1823.9(9) pm, β 96.51(2)° and R converged to 0.075 for 3542 observed reflections; structural parameters Pt-Cl 240(1), Pt-C(3) 212(2), Pt-P(2) (trans to Cl) 235(1) and Pt-P(1) (trans to CH2PPh3) 233(1) pm; Cl-Pt-C(3) 86.9(5), C(3)-Pt-P(2) 91.8(5), P(2)-Pt-P(1) 97.0(2) and P(1)-Pt-Cl 85.1(2)°. For X = I, a 1379.4(7), b 2044.4(10), c 1840.0(9) pm, β 96.09(2)° and R converged to 0.071 for 4333 observed reflections; structural parameters Pt-I 266(1), Pt-C(3) 212(2), Pt-P(2) (trans to I) 226(1) and Pt-P(1) (trans to CH2PPh3 233(1) pm; I-Pt-C(3) 87.2(5), C(3)-Pt-P(2) 91.5(5), P(2)-Pt-P(1) 96.5(2) and P(1)-Pt-I 85.6(1)°. Some other complexes of the type cis-[Pt(CH2PPh3)X(PPh3)2]Y are also described. 相似文献
The reaction of Cd(NO3)2 · 4H2O and Eu(NO3)3 · 6H2O or Tb(NO3)3 · 6H2O with potassium 3,5-di-tert-butylbenzoate (Kbzo) and N-donor ligands (1,10-phenanthroline (phen), 2,4-lutidine (2,4-lut), 3,4-lutidine (3,4-lut), phenanthridine (phtd), 2,3-cyclododecenopyridine (cdpy), acridine (acr)) afforded heterometallic LnCd2 complexes: [EuCd2(bzo)7(EtOH)2(phen)] (2), [LnCd2(bzo)7(2,4-lut)4] (Ln = Eu (3), Tb (4)), [EuCd2(bzo)7(H2O)2(2,4-lut)2] · MeCN (5), [EuCd2(NO3)(bzo)6(EtOH)2(2,4-lut)2] (6), [EuCd2(bzo)7(H2O)(EtOH)(3,4-lut)2] · 5EtOH (7), 3[EuCd2(bzo)7(H2O)2(phtd)2] · 4phtd (8), [EuCd2(bzo)7(EtOH)3(cdpy)] (9), 2[EuCd2-(bzo)2(EtOH)4] · acr (10). The structures of complexes 2, 3, and 5–10 were determined by single-crystal X-ray diffraction. The isostructurality of complexes 3 and 4 was confirmed by powder X-ray diffraction. The structure of the trinuclear {Ln2Cd} metal core is stable and independent of the type of peripheral ligands coordinated to cadmium atoms. Photoluminescent properties of compounds 3 and 4 were studied.
Four types of triblock glycols [(CL)4.5-PEG-(CL)4.5, (CL)4.5-PTAd-(CL)4.5, (CL)4.5-PTMG-(CL)4.5, and (CL)4.5-PPG-(CL)4.5, Mn=3,000] were synthesized by end-capping reactions of -caprolactone (CL) and poly(ethylene) glycol (PEG, Mn=2,000), poly(tetramethylene adipate) glycol (PTAd, Mn=2,000), poly(tetramethylene) glycol (PTMG, Mn=2,000), or polypropylene glycol (PPG, Mn=2,000)]. Waterborne polyurethanes (WBPUs) were prepared by polyaddition reaction using 4,4-dicyclohexylmethane diisocyanate (H12MDI), 2,2-bis (hydromethyl) propionic acid (DMPA), ethylene diamine (EDA), triethyl amine (TEA), and the triblock glycol. Studies have been conducted on the effects of triblock glycol type on the colloidal properties of dispersion, the hardness and mechanical properties of WBPU films, the water vapor permeability (WVP), and water resistance (WR) of WBPU-coated nylon fabrics. The WVP (%WVP based on control nylon fabric) of WBPU-coated nylon fabrics based on (CL)4.5-PEG-(CL)4.5, (CL)4.5-PTAd-(CL)4.5, (CL)4.5-PTMG-(CL)4.5 and (CL)4.5-PPG-(CL)4.5 were 3,975(81), 3,115(62), 3,124(64), and 2,569(52) g/m2 day (%), respectively. However, the WBPU based on (CL)4.5-PEG-(CL)4.5 was not applicable for coating material, because its dispersion and film had relatively high viscosity (3,000 cps at 50°C) and low mechanical properties, respectively. In this work, the triblock glycols (CL)4.5-PTMG-(CL)4.5 and (CL)4.5-PTAd-(CL)4.5 were found to be desirable glycols for water vapor permeable coating materials. 相似文献
The reactions of tricarbonylphosphine complexes (bipy)(P)Mo(CO)3, (bipy)= 2,2′-bipyridine and (P) = P(4-ClC6H4)3, P(4-FC6H4)3, P(4-CH3C6H4)3 and P(4-CH3OV6H4)3, with HgCl2 give compounds of the type (bipy)2Mo2(CO)6·HgCl2 and (bipy)Mo(CO)3(HgCl)(Cl), depending on the mol ratio of reactants employed. The reaction proceeds with elimination of the phosphine ligand and the coordination of HgCl2 to molybdenum.A new tricarbonyl complex (bipy)(dppe)2Mo2(CO)6 (dppe = 1,2-ethanediyl-bis(diphenylphosphine), with the bidentate phosphine ligand, is prepared from the reaction of the (bipy)Mo(CO)4 complex and dppe. The tricarbonyl-dppe derivative also reacts with HgCl2 in a 1:1 mol ratio, to give (bipy)(dppe)2Mo2(CO)6· 2HgCl2 and (dppe)3Mo2(CO)6·HgCl2. An excess of mercuric chloride yields the compound (bipy)(dppe)2Mo2(CO)6· 4HgCl2.In addition, the (bipy)Mo(CO)3(HgCl)(Cl) complex is isolated from the solution. 相似文献
Activation parameters have been obtained for the chelation of Mo(CO)5dpe (dpe = Ph2PCH2CH2PPh2) and of Mo(CO)5dmpe (dmpe = Me2PCH2CH2PMe2) to give cis-Mo(CO)4dpe and cis-Mo(CO)4dmpe respectively. The results are compared with those for the analogous chromium complexes and show that the enthalpy contribution determines the more rapid chelation in the molybdenum complexes. The preparation and properties of the chelate-bridged hetero-metallic complex (CO)5ModmpeMn(CO)4Br are reported. The reaction between Et4N[Mn(CO)4X2] (X = Cl, Br) and bidentate ligands dpe, dmpe and ape (ape = Ph2PCH2CH2AsPh2) in the presence of either silver(I) tetrafluoroborate or Et3OBF4 produces cis-Mn(CO)4X(bidentate) which is identified by infrared and mass spectrometry. At room temperature the Mn(CO)4X(bidentate) complex is rapidly converted to the chelated fac-Mn(CO)3X(bidentate) complex. The chelation process is approximately 104 times more rapid than in the isoelectronic chromium(O) complexes. The preparation and characterisation of fac-Mn(CO)3Br(dmpe), cis-Mn(CO)4Br(PMe3) and fac-Mn(CO)3Br(PMe3)2 are reported. 相似文献
Using Ni(Im)62+ (Im = imidazole) as the structural unit, the effects of oxygen-containing anions, such as SO42-, NO3? and CO32- on the structure of water clusters were studied. The crystal structures of three compounds [Ni(Im)6][SO4(H2O)11] (1), [Ni(Im)6][(NO3)Cl(H2O)4] (2), and [Ni(Im)6][CO3(H2O)5] (3) were obtained. Using Mercury-3.8 software to analyze the above three crystal structures, find different anion of water clusters had a significant effect on the supramolecular structure. At the same time, it also significantly influences the number of water molecules in the crystal structure. 相似文献
Complexes of CuHg(NCS)4, CuHg(NCS)2 (NCSe)2 and CuHg(NCSe)4 with tetrahydrofuran, dioxane, pyridine, 2-aminopyridine, nicotinamide, bipyridine and phenanthroline have been prepared and comparative studies made. Bipyridine and phenanthroline form cationic—anionic [CuL3]2+ [Hg(SCN)4]2? (L = bipy, phen) complexes with CuHg(NCS)4 and dinuclear bridged complexes with CuHg(NCSe)4 and CuHg(NCS)2 (NCSe)2. For other ligands the nature of the complexes is binuclear or polynuclear. The comparative stability of the -XCN- bridge (X = S, Se) is CuHg(NCSe)4 > CuHg(NCS)2 (NCSe)2 > CuHg(NCS)4. 相似文献
The kinetics and mechanisms of propadiene polymerization under the influence of [Rh(CO)2Cl]2, Rh(CO)2P(C6H5)3Cl, Rh(CO)3Cl are reported. The reaction rates are first-order in Rh(CO)2P(C6H5)3Cl and Rh(CO)3Cl and half-order in [Rh(CO)2Cl]2. They are second-order in the substrate for Rh(CO)3Cl and [Rh(CO)2Cl]2 and first-order for Rh(CO)2P(C6H5)3Cl. The data are interpreted in terms of a common intermediate mechanism. The formation of this common intermediate is the rate-determining step. A solvent effect is also discussed. 相似文献
From rehydration experiments the hydrates Ba(OH)2 · 8 H2O, Ba(OH)2 · 3 H2O β-Ba(OH)2, · 1 H2O, and γ-Ba(OH)2 · 1 H2O have been found in the system Ba(OH)2-H2O. Thermoanalytical measurements (DTA, TG, DTG, high temperature X-ray diffraction, high temperature Raman scattering) on these hydrates are reported. Thermal decomposition of Ba(OH)2 · 8 H2O and Ba(OH)2 · 3 H2O always results in the formation of β-Ba(OH)2 · 1 H2O, the stable form of the monohydrates at ambient temperature. Dehydration of β- and γ-Ba(OH)2 · 1 H2O, both of which form anhydrous β-Ba(OH)2 as the first product of decomposition, starts at 105 and 115°C, respectively. Single crystals of Ba(OH)2 · 3 H2O and γ-Ba(OH)2 · 1 H2O were prepared from Ba(OH)2 · 8 H2O meltings and from ethanolic solutions of Ba(OH)2 , respectively. The crystal data are: Ba(OH)2 · 3 H2O (orthorhombic, Pnma): a = 764.0(2), b = 1140,3(5), c = 596.5(1) pm, Z = 4; γ-Ba(OH)2 · 1 H2O (monoclinic, P21/m or P21): a = 704.9(2), b = 418.4(1), c = 633.3(1) pm, β = 111.45(2)°, Z = 2. 相似文献
