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1.
《Inorganica chimica acta》1988,146(1):25-31
The synthesis of organic polymers containing metal carbonyl moieties is described. The reaction of [Mo(CO)4(bipy)] with poly-4-vinylpyridine proceeds smoothly to give [Mo(CO)3(bipy)(poly-4-vinylpyridine)] which has a fac configuration. The thermal chemistry of a variety of polymer-bound metal carbonyl compounds is also presented, as is evidence for the formation of [W(CO)4(poly-4-vinylpyridinestyrene)] from [W(CO)5(poly-4-vinylpyridinestyrene)]. Included is evidence for the decarbonylation of polymer-bound metal compounds resulting in polymers which contain fully decarbonylated metal centres. Preliminary photochemical investigations indicate the generation of active coordinatively unsaturated metal carbonyl species in polymer matrices at low temperatures. 相似文献
2.
《Inorganica chimica acta》1986,116(2):99-107
Important theoretical approaches to metal cluster bonding including the Wade-Mingos skeletal electron pair method, the Teo topological electron count, the King-Rouvray graph theory derived method, and Lauher's extended Hückel calculations are shown to agree in their apparent skeletal electron counts for the most prevalent metal cluster polyhedra including the tetrahedron, the trigonal bipyramid (both ordinary and elongated), square pyramid, octahedron, bicapped tetrahedron, pentagonal bipyramid, and capped octahedron. The graph theory derived method is used to treat osmium carbonyl clusters containing from five to eleven osmium atoms. In this connection most osmium carbonyl clusters can be classified into the following types: (1) Clusters exhibiting edge- localized bonding containing multiple tetrahedral chambers (e.g., Os5(CO)16, Os6(CO)18, H2Os7(CO)20 and HOs8(CO)22−); (2) Capped octahedral clusters derived from osmium carbonyl fragments of the type Os6+p(CO)19+2p (p = 0, 1, 2, and 4) (e.g., Os6- (CO)182−, Os7(CO)21, Os8(CO)222−, and H4Os10- (CO)242−). Other more unusual osmium carbonyl clusters such as the planar Os6(CO)17 [P(OCH3)3]4, the Os9 cluster [Os9(CO)21C3H2R]−, and the Os11 cluster Os11C(CO)272− can also be treated satisfactorily by these methods. The importance of the number of ligands around isoelectronic Osn systems in determining the cluster polyhedron is illustrated by the different cluster polyhedra found for each member of the following isoelectronic pairs: HOs6- (CO)18−/H2Os6(CO)18. Os7(CO)21/H2Os7(CO)20, Os8(CO)222−/HOs8(CO)22−. The tendency for osmium carbonyl clusters frequently to form polyhedra exhibiting edge-localized rather than globally delocalized bonding relates to the facility for osmium carbonyl vertices to contribute more than three internal orbitals to the cluster bonding. In this way Wade's well-known analogy between boron hydride clusters and metal clusters, which assumes exactly three internal orbitals for each vertex atom, is frequently no longer followed in the case of osmium carbonyl clusters. 相似文献
3.
《Inorganica chimica acta》2006,359(11):3785-3789
The molecular structures of the dimeric cobalt compounds [Co(PPhMe2)(CO)3]2 and [Co2(PPhMe2)3(CO)5] have been characterised by X-ray crystallography. The compound [Co2(PPhMe2)3(CO)5] contains both bridging and terminal carbonyl groups in the solid state. 相似文献
4.
As part of a long-term study of the substitution reactions of piano-stool type cyclopentadienylmetal carbonyl complexes, several new methylcyclopentadienylmolybdenum compounds have been prepared and characterized by methods including IR spectroscopy, electrospray ionization mass spectrometry and X-ray crystallography. The complexes reported here include [{Cp′Mo(CO)3}2I]BPh4, cis-Cp′Mo(CO)2(PPh3)I and [Cp′Mo(CO)3(CH3CN)]BF4 (Cp′ = η5-C5H4CH3). In addition to their syntheses, comparisons are made between their IR spectroscopic and X-ray crystal structure data and those of similar complexes. 相似文献
5.
Martha T. de Araujo Eluzir P. Chacon José W. de M. Carneiro Andreas Koch Erich Kleinpeter 《Journal of molecular modeling》2010,16(8):1415-1420
Through-space NMR shieldings were calculated for trinuclear metal-carbonyl compounds [M3(CO)12] (M = Fe, Ru, Os), employing the nucleus-independent chemical shift approach. The through-space shieldings were visualized
as a contour plot of iso-chemical shielding surfaces, and were applied to quantify the overall anisotropic effect of the carbonyl
groups, as well as to identify the influence of the transition metal on the scopes of the corresponding anisotropy cones.
The shielding surfaces show that the anisotropic effect of the carbonyl groups at equatorial positions changes depending on
the metal. This effect was associated with π–backdonation from the metal to the carbonyl groups in that position, in agreement
with geometric data as well as calculated NMR parameters. Therefore, visualization of the through-space NMR shieldings of
trinuclear metal-carbonyl compounds of group 8 is able to reflect the distinct arrangements of the carbonyl groups in these
organometallic compounds. 相似文献
6.
A series of 14 aryl-substituted tetramethylcyclopentadienyl dinuclear metal carbonyl complexes have been synthesized by treating the corresponding ligands (C5Me4C6H4X-4) (X = H, Me, Cl, OMe) with Ru3(CO)12, Fe(CO)5, or Mo(CO)3(MeCN)3, respectively in refluxing xylene. It showed that the electronic effects of the substituents had influence on the molecular structures and reactions of the complexes, especially for the ruthenium and molybdenum complexes. In the reactions of aryl-substituted tetramethylcyclopentadiene with Mo(CO)3(MeCN)3, the electron-withdrawing effect of the substituent in the para position of benzene ring is favorable to produce the Mo-Mo triple bonded complexes, but the electron-donor effect of the substituent in the para position of benzene ring is favorable to produce the Mo-Mo single bonded complexes. In a given condition, the Mo-Mo single bonded complex could be transformed into the corresponding Mo-Mo triple bonded complex. The structures of nine complexes were determined by single crystal X-ray diffraction. 相似文献
7.
Photolysis of M2(CO)4(μ-S-t-Bu)2, where M = Rh or Ir, in Nujol matrices at ca. 90 K results in simple CO loss to form a tricarbonyl intermediate analogous to that observed for Rh2(CO)4(μ-Cl)2. Photolysis of the anions, [M(CO)2Cl2]1−, where M = Rh or Ir, in inert ionic matrices at ca. 90 K, results in CO-loss to form an intermediate analogous to that formed by Rh(CO)2(i-Pr2HN)Cl. Finally, photolysis of trans-Ir(CO)(PMe3)2Cl in a Nujol matrix at ca. 90 K gives rise to a new species whose carbonyl band is shifted slightly down in energy as has been observed for trans-Rh(CO)(PMe3)2Cl. In all cases the iridium compounds behave similarly to the rhodium species although the photon energy for iridium photochemistry is typically above that of the rhodium compounds. 相似文献
8.
Seiichi Homma Nobuko Suzuki Hiromichi Kato Masao Fujimaki 《Bioscience, biotechnology, and biochemistry》2013,77(6):876-883
Properties of ether extract of browned Kori-tofu were investigated. More than half amount of neutral glycerides of Kori-tofu changed into weak-acidic substances after browning, in which most of extracted brown pigments were contained. These weak-acidic substances showed properties of carbonyl and reductone, and mainly contained glycerides, whose constitutional fatty acids were palmitic, oleic, and linoleic acids as well as a little amount of azelaic and stearic acids.From the ether extract of browned Kori-tofu were isolated and identified azelaic acid and carbonyls. The carbonyls identified were benzaldehyde, methylethylketone, crotonal, acetaldehyde, α-ketoaldehydes of C2, C3, C4, C5, C7 and C9, and hexane-2,3-dione. Two nitrogeneous carbonyl compounds were isolated. Formation mechanisms of these compounds and their roles in browning of Kori-tofu were discussed. 相似文献
9.
《Inorganica chimica acta》1988,143(1):59-70
Complexes η-C5R5Fe(CO)2(η1-SC(S)OEt) (RH, (1) and RCH3 (2)) have been analysed by X-ray diffraction techniques. 1: P212121 11.3560(5), 10.8595(4), 10.1158(3) Å, Z=4; 1023 observed reflexions, R and Rw 0.069 and 0.073. 2: Pbca, 15.6907(11), 15.4566(13), 14.3083(11) Å, Z=8; 2271 observed reflexions, R and Rw being 0.071, 0.073. The coordination is quite similar for both compounds with the xanthate monodentate ligand almost perpendicular to the ring planes and a relative twist, one from each other of about 10°. The reductive electrochemistry of both complexes has been examined by cyclic voltammetry and coulometry. In a carbon electrode the first-one electron reduction step can be ascribed to the formation of corresponding carbonyl dimers. In a mercury electrode, the first reduction step of 1 leads to a bond rupture process with formation of a mercury compound [CpFe(CO)2]2Hg and further reduction to the anion CpFe(CO)2−. However, the behaviour of the pentamethylcyclopentadienyl complex (2) is quite different, and it is reduced in a three step process. 相似文献
10.
A methyl-detected ‘out-and-back’ NMR experiment for obtaining simultaneous correlations of methyl resonances of valine and isoleucine/leucine residues with backbone carbonyl chemical shifts, SIM-HMCM(CGCBCA)CO, is described. The developed pulse-scheme serves the purpose of convenience in recording a single data set for all Ileδ1, Leuδ and Valγ (ILV) methyl positions instead of acquiring two separate spectra selective for valine or leucine/isoleucine residues. The SIM-HMCM(CGCBCA)CO experiment can be used for ILV methyl assignments in moderately sized protein systems (up to ~100 kDa) where the backbone chemical shifts of 13Cα, 13Cβ and 13CO are known from prior NMR studies and where some losses in sensitivity can be tolerated for the sake of an overall reduction in NMR acquisition time. 相似文献
11.
《Inorganica chimica acta》1986,116(2):125-133
Previously discussed topological models of metal cluster bonding are now extended to the treatment of anionic rhodium carbonyl clusters having structures consisting of fused polyhedra. Examples of such rhodium carbonyl clusters built from fused octahedra include the ‘biphenyl analogue’ [Rh12(CO)30]−2, the ‘face-sharing naphthalene analogue’ [Rh9- (CO)19]3−, and the ‘perinaphthene analogue’, [Rh11- (CO)23]3−. More complicated anionic rhodium carbonyl clusters treated in this paper include the [Rh13(CO)24H5−q]q− anions (q = 2, 3, 4) having an Rh13 centered cuboctahedron, the [Rh14(CO)25- H4−q]q− (q = 3,4) and [Rh14(CO)26]2− anions based on a centered pentacapped cube, the [Rh15- (CO)30]3− anion having an Rh15 centered 14-vertex deltahedron, the [Rh15(CO)27]3− anion having a tricapped centered 11-vertex polyhedron, the [Rh17- (CO)30]3− anion having a tetracapped centered cuboctahedron, and the [Rh22(CO)37]4− anion having a hexacapped centered cuboctahedron fused to an octahedron so that the octahedron and the cuboctahedron share a triangular face. Analyses of the bonding topologies in [Rh9(CO)19]3−, [Rh17- (CO)30]3−, and [Rh22(CO)37]4− indicate that a polyhedral network containing several fused globally delocalized polyhedral chambers will not necessarily have a multicenter core bond in the center of each such polyhedral chamber. This observation is of potential importance in extending topological models of metal cluster bonding to bulk metals. 相似文献
12.
L. E. Muresan E. J. Popovici I. Perhaita E. Indrea J. Oro N. Casan Pastor 《Luminescence》2016,31(4):929-936
Yttrium aluminate (Y3A5O12) was doped with different rare earth ions (i.e. Gd3+, Ce3+, Eu3+ and/or Tb3+) in order to obtain phosphors (YAG:RE) with general formula,Y3‐x‐aGdxREaAl5O12 (x = 0; 1.485; 2.97 and a = 0.03). The synthesis of the phosphor samples was done using the simultaneous addition of reagents technique. This study reveals new aspects regarding the influence of different activator ions on the morpho‐structural and luminescent characteristics of garnet type phosphor. All YAG:RE phosphors are well crystallized powders containing a cubic‐Y3Al5O12 phase as major component along with monoclinic‐Y4Al2O9 and orthorhombic‐YAlO3 phases as the impurity. The crystallites dimensions of YAG:RE phosphors vary between 38 nm and 88 nm, while the unit cell slowly increase as the ionic radius of the activator increases. Under UV excitation, YAG:Ce exhibits yellow emission due to electron transition in Ce3+ from the 5d level to the ground state levels (2F5/2, 2F7/2). The emission intensity of Ce3+ is enhanced in the presence of the Tb3+ ions and is decreased in the presence of Eu3+ ions due to some radiative or non‐radiative processes that take place between activator ions. By varying the rare earth ions, the emission colour can be modulated from green to white and red. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
13.
Normen Szesni 《Inorganica chimica acta》2004,357(6):1789-1798
Photolysis of the allenylidene pentacarbonyl chromium complexes [(CO)5CrCCC(R1)R2] (R1=NMe2, NPh2; R2=NMe2, OMe, Ph) in THF in the presence of equimolar amounts of XR3 (XR3=various phosphanes, P(OMe)3, AsPh3, SbPh3) affords cis-allenylidene tetracarbonyl XR3 complexes, cis-[(CO)4(XR3)CrCCC(R1)R2]. When in the photolysis of [(CO)5CrCCC(NMe2)Ph], the phosphanes PR3 (R=C6H4F-p, C6H4Cl-p, OMe) are used in excess (three equivalents) two carbonyl ligands are displaced and the mer-tricarbonyl complexes mer-[(CO)3(PR3)2CrCCC(NMe2)Ph] are formed both PR3 ligands being mutually trans. The structure of the new complexes is established by IR, NMR, and UV-Vis spectroscopy, that of cis-[(CO)4(PPh3)CrCCC(NMe2)Ph] additionally by an X-ray structural analysis. As indicated by the spectroscopic data of the compounds, these complexes are best described as hybrids of allenylidene and zwitterionic alkynyl complexes with delocalization of the electron pair at nitrogen bonded to the Cγ atom of the allenylidene ligand towards the metal center. The relative contribution of the allenylidene and zwitterionic alkynyl resonance forms is influenced by XR3. Increasing the donor properties of XR3 favors the allenylidene resonance form. 相似文献
14.
《Inorganica chimica acta》1986,112(2):183-187
The fragmentation pathways of (η3-C3H4X)FeCO)2NO, (σ-C3H4X)Fe(CO)2(NO)L, (η3-C3H4X)Fe(CO)(NO)L, (σ-C3H4X)Fe(CO)2(NO)L′, (η3- C3H4X)Fe(CO)(NO)L′, (σ-C3H5)M(CO)5, (η3-C3H5)M(CO)4, (σ-CH2CHC(Me)2)Mn(CO)5, (η3-CH2 CHC(Me)2)Mn(CO)4, (X=2-Cl; L=PPh3; L′= P(OMe)3; M=Mn, Re) have been investigated by mass spectrometry. In the σ derivatives the molecular ion loses CO or the allylic ligand, while in the η3 derivative loss of a CO group is the only fragmentation mode of the molecular ion. Electron impact as well as methane chemical ionization mass spectra have been reported. Kinetic energy release of selected metastable ions indicates that a σ → η3 rearrangement reaction occurs. 相似文献
15.
Roshana T. Maske Atul N. Yerpude Rupesh S. Wandhare Sanjay J. Dhoble 《Luminescence》2023,38(10):1814-1824
The CaAlBO4:RE (RE = Dy3+, Eu3+, Sm3+) phosphor were prepared via combustion synthesis and studied by X-ray diffraction (XRD), Fourier-transform infrared (FTIR) analysis, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), photoluminescence (PL) spectra and CIE coordinates. The phase formation of the obtained phosphor was analyzed by XRD and the result was confirmed by standard PDF Card No. 1539083. XRD data successfully indicated pure phase of CaAlBO4 phosphor. The crystal structure of CaAlBO4 phosphor is orthorhombic with space group Ccc2 (37). The SEM image of CaAlBO4 phosphor reveals an agglomerated morphology and non-uniform particle size. The EDS image provides evidence of the elements present and the chemical makeup of the materials. Under the 350 nm excitation, the emission spectrum of Dy3+ activated CaAlBO4 phosphor consists of two main groups of characteristic peaks located at 484 and 577 nm which are ascribed to 4F9/2 → 6H15/2 and 4F9/2 → 6H13/2 transition of Dy3+ respectively. The PL emission spectra of CaAlBO4:Eu3+ phosphor shows characteristics bands observed around 591 and 613 nm, which corresponds to 5D0 → 7F1 and 5D0 → 7F2 transition of Eu3+ respectively, upon 395 nm excitation wavelength. The emission spectra of Sm3+ activated CaAlBO4 phosphor shows three characteristic bands observed at 565, 601 and 648 nm which emits yellow, orange and red color. The prominent emission peak at the wavelength 601 nm, which is attributed to 4G5/2 → 6H7/2 transition, displays an orange emission. The CIE color coordinates of CaAlBO4:RE (RE = Dy3+, Eu3+, Sm3+) phosphor are calculated to be (0.631, 0.368), (0.674, 0.325) and (0.073, 0.185). As per the obtained results, CaAlBO4:RE (RE = Dy3+, Eu3+, Sm3+) phosphor may be applicable in eco-friendly lightning technology. 相似文献
16.
Reaction of (acetonitrile)-nona(carbonyl)-di-manganese and tri-iso-propyl phosphite provided the new phosphite compound [Mn2(CO)9L]. The product was fully characterized and the molecular structure was determined by single crystal X-ray diffraction. This represents the first structural analysis of a di-manganese carbonyl compound containing phosphite ligands. In addition, this compound displays a rare example of an equatorially substituted di-manganese carbonyl compound. 相似文献
17.
Mariana Tinajero-Trejo Katie J. Denby Svetlana E. Sedelnikova Shahira A. Hassoubah Brian E. Mann Robert K. Poole 《The Journal of biological chemistry》2014,289(43):29471-29482
CO and NO are small toxic gaseous molecules that play pivotal roles in biology as gasotransmitters. During bacterial infection, NO, produced by the host via the inducible NO synthase, exerts critical antibacterial effects while CO, generated by heme oxygenases, enhances phagocytosis of macrophages. In Escherichia coli, other bacteria and fungi, the flavohemoglobin Hmp is the most important detoxification mechanism converting NO and O2 to the ion nitrate (NO3−). The protoheme of Hmp binds not only O2 and NO, but also CO so that this ligand is expected to be an inhibitor of NO detoxification in vivo and in vitro. CORM-3 (Ru(CO)3Cl(glycinate)) is a metal carbonyl compound extensively used and recently shown to have potent antibacterial properties. In this study, attenuation of the NO resistance of E. coli by CORM-3 is demonstrated in vivo. However, polarographic measurements showed that CO gas, but not CORM-3, produced inhibition of the NO detoxification activity of Hmp in vitro. Nevertheless, CO release from CORM-3 in the presence of soluble cellular compounds is demonstrated by formation of carboxy-Hmp. We show that the inability of CORM-3 to inhibit the activity of purified Hmp is due to slow release of CO in protein solutions alone i.e. when sodium dithionite, widely used in previous studies of CO release from CORM-3, is excluded. Finally, we measure intracellular CO released from CORM-3 by following the formation of carboxy-Hmp in respiring cells. CORM-3 is a tool to explore the concerted effects of CO and NO in vivo. 相似文献
18.
D CourtneyN.L Cromhout D CunninghamJ.F Gallagher A.R Manning P McArdleS.I Pratt 《Inorganica chimica acta》2002,327(1):98-107
The iron hydrido complex HFe(CO)2{P(OPh)3}{(PhO)2POC6H4} (1), was rapidly deprotonated by DBU or [BzMe3N][OH] in THF to afford the new carbonyl iron anion [Fe(CO)2{P(OPh)3}{(PhO)2POC6H4}]− ([2]−), containing an ortho-metallated triphenyl phosphite ligand. Complex [2]− reacted with triorganostannyl and plumbyl salts and with halogens to give the octahedral FeII compounds Fe(CO)2{P(OPh)3}{(PhO)2POC6H4}(X) (X=SnPh3, 3; SnMe3, 4; PbPh3, 5; PbMe3, 6; Cl, 7; Br, 8; I, 9). The Group 14 complexes 3-6 were obtained in one isomeric form in which the PIII-donor atoms are mutually cis, the carbonyl ligands are cis and the P(OPh)3 and MR3 (M=Sn, Pb; R=Ph, Me) groups are trans as determined by solution-state IR, 31P and 13C NMR spectroscopic data. This geometry was confirmed for 3 by a single crystal X-ray diffraction study. The halide complexes, however, were obtained as a mixture of isomers. The major isomer (7, X=Cl; 8a, X=Br; 9a, X=I) has cis P atoms, trans CO groups and the halide located trans to the phosphorus atom of the ortho-metallated phosphite ligand. The structure of 9a was confirmed by an X-ray diffraction study. Two other isomers, designated 8b (X=Br) and 9b (X=I), with cis P atoms and cis CO groups were isolated from the reactions of [2]− with Br2 and I2, respectively. The structure of the latter was established by X-ray crystallography and is related to 9a by exchange of the P(OPh)3 ligand and a carbonyl group such that the metal-bound C atom of the five-membered metallacycle is trans to CO. The stereo-geometry of 8b could not be unambiguously assigned from the spectroscopic data; however, two of the seven possible geometric isomers were suggested as plausible structures. 相似文献
19.
Ruthenium phosphine complexes with a CO ligand [Ru(tpy)(PR3)(CO)Cl]+ (tpy = 2,2′:6′,2″-terpyridine, R = Ph or p-tolyl), were prepared by introduction of CO gas to the corresponding dichloro complexes at room temperature. New carbonyl complexes were characterized by various methods including structural analyses. They were shown to release CO following the addition of several N-donors to form the corresponding substituted complexes. The kinetic data and structural results observed in this study indicated that the CO release reactions proceeded in an interchange mechanism. The molecular structures of [Ru(tpy)(PPh3)(CO)Cl]PF6, [Ru(tpy)(P(p-tolyl)3)(CO)Cl]PF6 and [Ru(tpy)(PPh3)(CH3CN)Cl]PF6 were determined by X-ray crystallography. 相似文献
20.
Saija LuukkanenMatti Haukka Olli LaineTapani Venäläinen Pirjo VainiotaloTapani A Pakkanen 《Inorganica chimica acta》2002,332(1):25-29
Chlorine containing ruthenium bipyridine carbonyl compounds react readily in dilute alkaline solutions under a CO atmosphere affording a poorly soluble and air sensitive product that is suggested to have a polymeric nature. Various analysis methods (MS and TPD) were used in the characterisation of the product. The replacement of the axial chloride ligands in trans(Cl), cis(CO)[Ru(bpy)(CO)2Cl2] and [Ru(bpy)(CO)2Cl]2 is proposed to be the initial step in the polymerisation. The replacement of chlorides in methanolic solution was confirmed by isolating and characterising the dimeric intermediate [Ru(bpy)(CO)2(COOCH3)]2. 相似文献