A new molybdenum(0) dithiocarbamato complex [Et4N] [Mo(CO)4(S2CNEt2)] (1) has been synthesized by the reaction of Mo(CO)6, NaS2CNEt2 and Et4NCl in MeCN and characterized by routine elemental analysis, spectroscopy methods. The crystal and molecular structure of 1 was determined from X-ray three dimension data. 1 crystallizes in the orthorhombic, space group Pbc21 with a= 8.148(2), b=19.618(2), c=14.354(2) Å; V=2294 Å3; Z=4; R1=0.052, R2=0.058 for 1308 independent reflections with I ⩾ 3σ(I). The geometry around Mo(0) atom in the anion [Mo(CO)4(S2CNEt2)]- of 1 is distorted octahedral with a small SMoS of 67.70° and a small angle of 3.6° between plane MoSS and MoC(1)C(2). Two groups of MoCO bond distances and the longer MoS bond distance observed in 1 are similar to that in the dinuclear Mo(0) complexes containing SR bridges but very different from those observed in the dithiocarbamato complexes of Mo in higher oxidation states. Different oxidizing products containing Mo in II-V oxidation states Mo(CO)2(S2CNEt2)2, MoO(S2CNEt2)2, Mo2O3(S2CNEt2)4 and Mo2O4(S2CNEt2)2 were isolated from the oxidation of 1 with I2 (or in the presence of traces of air). The electrochemical behavior of 1 in MeCN was investigated by cyclic voltammetry at Pt and C electrodes. The anodic peaks observed at 0.04, 0.14, 0.26 and 0.44 V versus SCE implied that 1 probably underwent oxidation in company with dissociation of dithiocarbamate and substitution of carbonyls resulting in several complexes of Mo in different oxidation states. The relationship between reactivity and structure is also discussed. 相似文献
Reaction of Mo2(O2CCH3)2(DMepyF)2 (HDMepyF=N,N′-di(6-methyl-2-pyridyl)formamidine) with HBF4 in CH2Cl2/CH3CN afforded the complex trans-[Mo2(H2DMepyF)2(CH3CN)4](BF4)6 (1), which crystallized in two forms, trans-[Mo2(H2DMepyF)2(CH3CN)4](ax-CH3CN)2(BF 4)6 · 2CH3CN (1a), and trans- [Mo2(H2DMepyF)2(CH3CN)4](ax-BF4) 2(BF4)4 · 2CH3CN (1b). The molecular structures of complexes (1) consist of two quadruply bonded molybdenum atoms, which are spanned by two trans-bridging formamidinate ligands and coordinated by four trans-CH3CN. Each H2DMepyF+ ligand adopts an s-cis,s-cis- conformation. The difference between 1a and 1b is that complex 1a contains two CH3CN molecules as axial ligands, while 1b contains two BF4− anions as axial ligands. Complex 1 is the first dimolybdenum complex containing a pair of trans bridging ligands and two pairs of trans-CH3CN ligands. 相似文献
Reaction of cis-[Mo2(OAc)2(CH3CN)6][BF4]2 with NP-Et,Me (2-ethyl-3-methyl-1,8-naphthyridine) in acetonitrile provides trans-[Mo2(NP-Et,Me)2(OAc)2(CH3CN)][BF4]2 (1). Partial protonation of 1 by HBF4·Et2O in acetonitrile leads to trans-[Mo2(NP-Et,Me)2(OAc)(CH3CN)3][BF4]3 (2). In both compounds, NP-R ligands are arranged in a head-to-head (HH) fashion leaving one of the axial sites vacant. Substitution of acetonitriles by NP-Me (3-methyl-1,8-naphthyridine) in trans-[Mo2(NP-tz)2(OAc)(CH3CN)2][BF4]3 provides trans-[Mo2(NP-tz)2(OAc)(NP-Me)][BF4]3 (3) with retention of configuration. Fully solvated dimolybdenum(II) compound reacts with NP-NH2 to provide [Mo2(NP-NH2)2(NP-NH)(CH3CN)2][BF4]3 (4) in which the NP-NH2 ligands are trans and arranged in a HH fashion. The deprotonated ligand (NP-NH−) binds the dimetal unit utilizing naphthyridine nitrogen and amido nitrogen. Treatment of [Mo2(NP-tz)2(CH3CN)4][CF3SO3]4 with bpym (2,2′-bipyrimidine) followed by crystallization in air provided an oxo complex [Mo2(NP-tz)2(μ2-O)2(bpym)2][CF3SO3]4 (5). Compounds 1-5 have been characterized by a variety of spectroscopic techniques and by X-ray crystallography. The reactivity pattern is rationalized based on ligand labilities and thermodynamic stabilities. 相似文献
Four novel Mo(II) and Rh(II) complexes with cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl)ethene (cis-dbe) or closed-dbe were synthesized and characterized. Employing [M(O2CCF3)4] (M = Mo, Rh) with cis-dbe or closed-dbe afforded complex [Mo2(O2CCF3)4(cis-dbe)](benzene) (1), [Rh2(O2CCF3)4(cis-dbe)](benzene) (2), [{Mo2(O2CCF3)4}2(closed-dbe)] (3), and [Rh2(O2CCF3)4(closed-dbe)](p-xylene) (4). The structures of four metal complexes were revealed by X-ray crystallographic analyses and the correlation between the crystal structures and the photochromic performance was discussed. In all complexes, two cyano groups of the ligand bridged two dimetal carboxylates to give a 1-D zigzag infinite chain structure. Upon irradiation with 405 nm light, complex 1 turned into reddish purple from yellow, and the color reverted to initial yellow on exposure to 563 nm light, indicating the reversible cyclization/ring-opening reaction in the crystalline phase. However, the Rh(II) complex 2 did not display similarities in reaction induced by light, which is attributable to the lower ratio of photoactive anti-parallel conformers compared with complex 1 and coordination effect of metal ions on photochromism of diarylethenes. The complexes of Rh(II) ions did not exhibit the expected reversible photoinduced behavior. 相似文献
Mo(CO)4(LL) complexes, where LL = polypyridyl ligands such as 2,2′-bipyridine and 1,10-phenanthroline, undergo quasi-reversible, one-electron oxidations in methylene chloride yielding the corresponding radical cations, [Mo(CO)4(LL)]+. These electrogenerated species undergo rapid ligand substitution in the presence of acetonitrile, yielding [Mo(CO)3(LL)(CH3CN)]+; rate constants for these substitutions were measured using chronocoulometry and were found to be influenced by the steric and electronic properties of the polypyridyl ligands. [Mo(CO)3(LL)(CH3CN)]+ radical cations, which could also be generated by reversible oxidation of Mo(CO)3(LL)(CH3CN) in acetonitrile, can be irreversibly oxidized yielding [Mo(CO)3(LL)(CH3CN)2]2+ after coordination by an additional acetonitrile. Infrared spectroelectrochemical experiments indicate the radical cations undergo ligand-induced net disproportionations that follow first-order kinetics in acetonitrile, ultimately yielding the corresponding Mo(CO)4(LL) and [Mo(CO)2(LL)(CH3CN)3]2+ species. Rate constants for the net disproportionation of [Mo(CO)3(LL)(CH3CN)]+ and the carbonyl substitution reaction of [Mo(CO)3(LL)(CH3CN)2]2+ were measured. Thin-layer bulk oxidation studies also provided infrared characterization data of [Mo(CO)4(ncp)]+ (ncp = neocuproine), [Mo(CO)3(LL)(CH3CN)]+, [Mo(CO)3(LL)(CH3CN)2]2+ and [Mo(CO)2(LL)(CH3CN)3]2+ complexes. 相似文献
The crystal structure of the dimeric Ag maleonitriledithiolate complex, Ag2[S2C2(CN)2] [P(C6- H5)3]4 (1), has been performed. Complex 1 crystallizes in the space group P21/c with a = 12.2898(77), b = 23.8325(91), c = 23.1790(118) Å, β = 101.315(43)° and Z = 4. Refinement using 3253 reflections with Fo2>3σ(Fo2) yielded R = 0.0662, Rw= 0.0669. The most interesting aspect of the structure is the strong bridging interaction of the chelating maleonitriledithiolate ligand with the second Ag center, where a Ag-S distance of 2.478 Å is observed. The residual bonding capability of the sulfur atoms in the chelating anion [Ag(S2C2(CN)2)(PPh3)2]− for [Ag(PPh3)2]+ is demonstrated. 相似文献
The crystal structure of Mo2O5[SC6H4NHCH2C5H4N]2(C3N7NO)3 is reported and seen to consist of a single oxo-bridged species with each Mo atom bonded to cis dioxo groups and the nitrogen atoms and thiolate group of the tridentate ligand. 95Mo NMR spectra of this and three related complexes are presented and attempts made to interpret them in terms of their crystal structures. 相似文献
The reaction of 2-(methylthioethanol) with 1,8-dichloroanthraquinone and 1,5-dichloroanthraquinone in THF with base produces 1,8-bis(2-methylthioethoxy)anthraquinone (1) and 1,5-bis(2-methylthioethoxy)anthraquinone (2), respectively. Silver(I) complexes of 1 and 2 have been synthesized after combination with [Ag(CH3CN)4]BF4 in 1:1 M ratio to yield, [(1,8-bis(2-methylthioethoxy)anthraquinone)Ag]BF4, (3) and [(1,5-bis(2-methylthioethoxy)anthraquinone)Ag·CH3CN]BF4, (4). X-ray crystal structures of the free ligand (1) and the Ag(I) complexes (3 and 4) are reported. The intraannular carbonyl group forms a coordinate-covalent bond with Ag(I) and, in the solid state, both silver(I) complexes are found as coordination polymers. 相似文献
Complexes of the M(en)3Ag2(CN)4 (M = Ni, Zn, Cd) and M(en)2Ag2(CN)4 (M = Ni, Cu, Zn, Cd) type were prepared and identified by elemental analysis, infrared spectroscopy, measurement of magnetic susceptibility, and X-ray powder diffractometry. The crystal structures of Ni(en)3Ag2(CN)4 (I) and Zn(en)2Ag2(CN)4 (II) were determined by the method of monocrystal structure analysis. Complex I crystallizes in the space group C2/c, a = 1.2639(5), b = 1.3739(4), c = 1.2494(4) nm, β = 113.25(4)°, Dm = 1.86(1), Dc = 1.86 gcm−3Z = 4, R = 0.0429. The crystal structure of I consists of complex cations [Ni(en)3]2+ and complex anions [Ag(CN)2]−. Complex II crystallizes in the space group I2/m, a = 0.9150(3), b = 1.3308(4), c = 0.6442(2) nm, β = 95.80(3)°, Dm = 2.14(1), Dc = 2.15 gcm−3, Z = 2, R = 0.0334. Its crystal structure consists of infinite, positively charged chains of the [-NCAgCNZn- (en)2]nn+ type and isolated [Ag(CN)2]− anions. The atoms of Ag are positioned parallely to the z axis and the AgAg distance is equal to 0.3221(2) nm. 相似文献
Use and application of Schiff bases are extended to many different fields of technology. (ISE)M(CO)5 complex [M?=?Cr (1), Mo (2), W (3), and where ISE is 3[4-ethyl(phenly)imino][indoline-2-one]; and (ISB)M(CO)5 [M?=?Cr (4), Mo (5), W (6)], where ISB is 3[4-butly(phenly)imino][indoline-2-one] were investigated by computational methods. Computations were carried out using density functional theory (DFT) with B3LYP and CAM-B3LYP functionals, in conjunction with LanL2DZ basis set for metals and cc-PVTZ basis set for other atoms. Time-dependent density functional theory (TDDFT) was used at the same level to obtain the electronic transitions. Molecular orbital energies, UV-Vis spectra, and total electron densities of investigated molecules were shown in the gas phase and in THF. Metal complexes showed higher absorption coefficients compared to ISE and ISB in the visible region. Additionally, they displayed absorption peaks at longer wavelengths and full MLCT character in solution, and W complexes required less energy compared to the complexes of other investigated metal ions. Among the investigated systems, (ISE)W(CO)5 and (ISB)W(CO)5 complexes with lowest HOMO-LUMO gaps are found to be the best candidates for photosensitive material production.
Two new heterometallic complexes, [Cu(en)(H2O)]2[Fe(CN)6]·4H2O (1) and [Cu(en)2][KFe(CN)6] (2), have been isolated from the reactions of CuCl2 and en with K3[Fe(CN)6] in different molar ratios. Both complexes have been characterized by X-ray analyses, IR spectra and elemental analyses. Complex 1 is a cyanide bridged bimetallic assembly, its crystal structure consists of a two-dimensional polymeric sheet with two different rings, one a four-membered square ring and another a 12-membered hexagonal ring. The Fe(II) ion of 1 has two terminal, two linear bridging and two 1,1 en-on bridging cyanide groups. In the crystal structure of 2, the neighboring [Fe(CN)6]3− units are bridged by the K+ and the [K[Fe(CN)6]]2− units forming a three-dimensional network structure. The [Cu(en)2]2+ units fill in the holes of the network acting as counter cations and charge compensations. Variable temperature magnetic susceptibility studies of 1 indicate that the complex exhibits ferromagnetic interaction between the Cu(II) ions. 相似文献
The iridium(III) dihydride complexes IrH2X- (Cyttp) (X = Cl, I) possess a mer-octahedral structure in which the hydrides are cis to each other and the Cyttp ligand is chelated around an edge of the octahedron. The phenyl group on the central phosphorus atom is oriented away from the chloride ligand in the crystal structure, and Nuclear Overhauser Effect (NOE) measurements show that this anti coordination geometry is maintained in solution. Treatment of IrH2Cl(Cyttp), 1a, with TIBF4 and CH3CN results in a mixture of anti and syn diastereomers, whereas CO gives only the syn diastereomer of the type [IrH2(CH3CN)(Cyttp)]+ and Tl+. 相似文献
A new compound of formula [Fe(qsal)2][Ni(dmit)2] (1) has been synthesised, structurally and magnetically characterised (qsalH = N-(8-quinolyl)salicylaldimine, dmit2− = 1,3-dithiol-2-thione-4,5-dithiolato). Its structural features and its magnetic behaviour were compared with those of [Fe(qsal)2]-based complexes, and more particularly [Fe(qsal)2][Ni(dmit)2] · 2CH3CN. 相似文献
The reaction of the ruthenium complexes RuCl2(PPh3)3, RuCl2(PPh3)4, RuCl2(PMe3)4, RuCl2(Me2SO)4, or RuBr2(PPh3)3 with the tripod tetrakis(tertiary) phosphine P(CH2CH2CH2PMe2)3 gave the compounds cis-RuCl2 [P(CH2CH2CH2PMe2)3] (1) and cis-RuBr2[P(CH2CH2CH2PMe2)3] (2). The coordination geometry of 1 and 2 was derived from the ABX2 type 31P NMR patterns of the complexes, as well as from an X-ray structure determination for the chloride 1. Crystals of 1 were found to be monoclinic, space group P21/n (Z = 4), with a = 942.0(3), b = 1446.2(4), c = 1680(1) pm, and β = 104.99(4)°. Anisotropic refinement of the structure converged at R = 0.040 and Rw = 0.034 (3318 data). Selected bond lengths are (in pm): RuP(CH2−)Me2 (trans-atom P), 235.8(1) and 239.3(1); RuP(CH2−)Me2 (trans-atom Cl), 227.9(1); RuP(CH2−)3, 225.3(1); RuCl (trans-group P(CH2−)3), 252.1(1); and RuCl (trans-group P(CH2)Me2), 250.5(1). Reaction of 1 with LiAlH4 yielded the hydro derivatives cis-Ru(H)Cl[P(CH2CH2CH2PMe2)3] (3) and cis-RuH2[P(CH2CH2CH2PMe2)3] (4), which were characterized by IR and 1H and 31p NMR spectroscopy. 相似文献
Bimetallic alkylidene complexes of molybdenum (RF3O)2(ArN)MoCH-SiMe2-CHMo(NAr)(ORF3)2 (1) and (RF3O)2(ArN)MoCH-SiPhVin-CHMo(NAr)(ORF3)2 (2) (Ar = 2,6-C6H3; RF3 = CMe2CF3) have been prepared by the reactions of vinyl silicon reagents Me2Si(CHCH2)2 and PhSi(CHCH2)3 with known alkylidene compound PhMe2C-CHMo(NAr)(ORF3)2. Complexes 1 and 2 were structurally characterized. Ring opening metathesis polymerization (ROMP) of cyclooctene using compounds 1 and 2 as initiators led to the formation of high molecular weight polyoctenamers with predominant trans-units content in the case of 1 and predominant cis-units content in the case of 2. 相似文献
The first heterometallic chain cluster {[Mn4(hmp)6(NO3)2FeNO(CN)5·4CH3CN}n (1) based on the [Mn4(hmp)6] SMM has been synthesized. 1 has one-dimensional chain structure: the [Mn4(hmp)6] units are linked via CN-groups of nitroprusside anions. Its magnetic and relaxation properties and low temperature IR spectra under light irradiation have been investigated. The ferromagnetic exchange constants have been calculated. 相似文献
The organometallic Lewis acid, [CpFe(CO)2]+ (Cp = η5-C5H5) reacts with excess dry diethyl ether at low temperatures to form the labile complex [CpFe(CO)2(Et2O)]+[BF4]− (1) which is stable at low temperatures and has been fully characterized. Complex 1 in turn reacts with 1-aminoalkanes and α,ω-diaminoalkanes to form new complexes of the type [CpFe(CO)2NH2(CH2)nCH3]BF4 (n = 2-6) (2) and [{CpFe(CO)2}2μ-(NH2(CH2)nNH2)](BF4)2 (n = 2-4) (3), respectively. These complexes have been fully characterized and the mass spectral patterns of complexes 2 are reported. The structures of compounds 2a (n = 2) and 2b (n = 3) have been confirmed by single crystal X-ray crystallography. The single crystal X-ray diffraction data show that complex 2a, [CpFe(CO)2NH2(CH2)2CH3]BF4, crystallizes in a triclinic space group while 2b, [CpFe(CO)2NH2(CH2)3CH3]BF4, crystallizes in an orthorhombic Pca21 space group with two crystallographically independent molecular cations in the asymmetric unit. Furthermore, the reaction of 1 with 1-alkenes gives the η2-alkene complexes in high yield. 相似文献
The complexes [Cu2(dppa)3(CH3CN)2][BF4]2 (1) and Cu2(dppa)3(O3SCF3)2 (2) have been prepared in good yields by treating [Cu(MeCN)4][BF4] and [Cu(MeCN)4][O3SCF3], respectively, with Ph2PCCPPh2 (abbreviated as dppa) at room temperature. The reaction of 1 with di-2-pyridyl ketone (abbreviated as dpyk) produces [Cu2(dppa)2(dpyk)2][BF4]2 (3), and with 1,1′-bis(diphenylphosphino)ferrocene (abbreviated as dppf) produces [Cu2(dppa)(dppf)2][BF4]2 (4). The molecular structures of 1-4 have been determined by an X-ray diffraction study. Compounds 1 and 2 form a helical Cu2(dppa)3 metallatricycle, compounds 3 forms a Cu2(dppa)2 metallacycle, and compound 4 contains a linear Cu2(dppa) skeleton. 相似文献
Reaction of the cluster salt [(η5-Cp′)3Mo3S4][pts] ([1][pts], Cp′=methylcyclopentadienyl; pts=p-toluenesulfonate) with CuCl yielded a new heterobimetallic cluster, [(η5-Cp′)3Mo3S4Cu(Cl)][pts] ([2][pts]). X-ray crystal structure determination of [1][pts] and [2][pts] showed that the incorporation of CuCl into the Mo3S4 cluster core has only minor consequences on the Mo-Mo and Mo-S distances. The metal atoms in the cluster core of [2]+ form an almost regular tetrahedron. The [2]+ cation conforms to an idealized C3v symmetry ignoring the Cp′ groups since the Cu-Cl bond is almost aligned with the axis defined by the Cu-S(4) cube diagonal. 相似文献
The bimetallic [M1M2(tren)2(CAn?)]m+ series, where M = GaIII or CrIII and CA is the chloranilate ligand which can take on diamagnetic (CAcat,cat)4? or paramagnetic (CAsq,cat)3? forms, comprises an electronically diverse series of compounds ranging from the closed-shell [Ga2(tren)2(CAcat,cat)]2+ to the S = 5/2 ground state of [Cr2(tren)2(CAsq,cat)]3+. This report deals with the interpretation of the EPR and ENDOR spectra of [Ga2(tren)2(CAsq,cat)](BPh4)2(BF4) (2) and the related derivative [Ga2(tren)2(DHBQ)](BPh4)2(BF4) (2a) (where DHBQ is the fully deprotonated trianionic form of 2,5-dihydroxy-1,4-benzoquinone) in an effort to further characterize the electronic structure of this radical species. The X-band (～9.5 GHz) EPR spectrum of complex 2 acquired in a butyronitrile/propionitrile glass at 4 K reveals a rhombic g-tensor with gxx = 2.0100, gyy = 2.0097, and gzz = 2.0060 with hyperfine interactions due to spin delocalization onto the two Ga nuclei (axx = 4.902 G, ayy = 4.124 G, azz = 3.167 G); the origin of the hyperfine coupling was confirmed by analysis of the room temperature spectra of complexes 2 and 2a. The low-temperature spectrum of complex 2 also indicates the presence of a triplet electronic state characterized by a g-value of 2.009 and axial zero-field splitting of D = 150 G (0.012 cm?1) as determined from measurements carried out at both X- and W-band (～95 GHz) frequencies. This triplet state is believed to arise due to a weak intermolecular Heisenberg exchange interaction between two aggregating complexes. ENDOR measurements on complex 2a at 20 K allowed for a determination of the magnitude of hyperfine coupling to the protons associated with the radical bridge as well as providing a rare example of an ENDOR signal arising from coupling to a gallium nucleus. Finally, these results were combined with literature data on the free semiquinone form of the bridging ligand in order to assess the extent to which density functional theory can predict unpaired spin density distribution in a complex molecule of this type. Although differences between theory and experiment were noted, DFT was able to provide a reasonably accurate picture of the electronic structure of this system as well as provide insight into the spin polarization mechanism(s) responsible for the observed hyperfine interactions. 相似文献
