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Complexes nitrosyl

Nitrosyl Complexes.—Cr(NO)4 is formed when a slow stream of NO is drawn through an irradiated solution of Cr(CO)6 in a hydrocarbon solvent. The compound has been characterized by i.r., Raman, and mass spectral studies and shown to be a simple molecular species. The occurrence of only one v(N—O) stretching mode (1716 cm in the i.r. and the occurrence of two [Pg.94]

A direct, quantitative, and convenient method for the preparation of [Cr(H20)5N0] has been achieved by the slow, dropwise addition of an aqueous solution of Cr° (10 ml, 0.5 mol 1 ) to a stirred solution of HCIO4 (200 ml, 0.1 mol 1 ) which was continuously saturated with NO. This reaction is rapid and produces only [Cr(H20)5N0] , provided that NO is in excess. This study also confirmedthe previously reported d-d spectrum of this ion. Several e.s.r. studies of chromium nitrosyl complexes containing a variety of other ligands have been reported. The i.r.-polarized spectra of K3[Cr(CN)5N0],2H20 have been determined and the results strongly support the suggestion that the orientation of the anions is disordered. The salts K4[M(CN)5N0] (M = Cr or Mo) appear to be isomorphous and the assignment of the vibrational modes in these ° and related compounds has been discussed.  [Pg.95]

Nitrosyl Complexes. The effects of the ligands and central atoms on the integral intensities of v(NO) have been studied in the series [Ru(NO)X5] (X = Cl, Br, or I), [Ru(NO)(NH3)4X ]-+ (X = NH3 or OH) and [M(NO)(CN)5] (M = Ru or Os). Band intensities for v(NO), v(RuN), and v(RuCl) have been calculated using a harmonic oscillator approximation and potential energy curves obtained by CNDO calculations on [Ru(NO)C1 (NH3)5 P The intensity of v(NO) decreases as the overall charge is made more positive, and experimental values of the v(NO) intensity are considered to be a measure of the Ru — NO 7r-donation. CNDO calculations have also been performed on [Ru(NO)X5] (X = H2O, NH3, Cl, or CN ) and used to assess the T-donor properties of the ligands (NO ii H20 NH3 C1 CN ).  [Pg.308]

Heteropoly-complexes containing (RuNO) (n = 2 or 3) have been characterized, and electron transfer between isostructural pairs has been studied. Treatment of Bao.s[Ru(LH2)3] (LH3 = NHC0C(N0H)C0NH( 0) with NaN02 in acidic solutions yields the six-co-ordinate [Ru(LH2)3(NO)] one LHJ ligand is displaced by Cl or Br . Hydrolysis of [Ru(NH3)5NO] in 0.1 M aqueous NaOH for 7 days gives rise to [Ru(NH3)5N2], and cis- and trans-[Ru(OHXNO)(NH3)4].  [Pg.308]

Nitrosyl Complexes.—A ledetmnination of the structure of twinned crystals of nitrosylpenta-anuninccobalt dichloride establishes that the Co-N-O angle is 119.0(9)° rather than close to 180° as was found in previous studies. The Co-N(NO) distance of 1.871(6) A is considered long. The [Pg.556]

88(1) A in (47a) and (47b) respectively are only slightly longer than the corresponding Co-N(NO) distances.  [Pg.558]

The crystal structure of dinitrosylcobalt nitrite contains polymeric chains (48) linked through nitrite Co-N-O-Co bridges. Each cobalt atom is [Pg.558]

Few complexes containing only nitrosyl ligands are well characterized, but many mixed carbonyl-nitrosyl complexes are known.41 They may be formed readily by replacement oF carbon monoxide with nitric oxide  [Pg.650]

Unlike carbon monoxide, which can be used in excess at high temperatures and pressures, nitric oxide in excess can cause unfavorable oxidation, and at high pressures and temperatures it decomposes. Many of the current syntheses avoid the use oF nitric oxide by substituting nitrosyl chloride, nitrites, or nitrosonium salts 42 [Pg.650]

Although the nitrosyl group generally occurs as a terminal ligand, bridging nitro-syls are also known  [Pg.650]

As in the case of the corresponding carbonyl complexes, infrared stretching frequencies are diagnostic of the mode oF coordination.43 For the product in Eq. 15.38. v (terminal NO) = 1672 cm-1 and v (bridging NO) = 1505 cm-1. [Pg.650]

41 Except for CriNO).. no binary metal nitrosyl complexes have been obtained in pure form. Guest. [Pg.650]

In the oxidation state method, the ligand is viewed as a coordinated nitrosyl ion. NO, when linear and a coordinated NO when bent it is a two-electron donor in both forms. [Pg.651]

Ruthenium probably forms more nitrosyl complexes [115] than any other metal. Many are octahedral Ru(NO)X5 systems, where X5 can represent a combination of neutral and anionic ligands these contain a linear (or very nearly) Ru—NO grouping and are regarded as complexes of ruthenium(II). They are often referred to as Ru(NO) 6 systems. [Pg.43]

Two types of NO coordination to ruthenium are known linear Ru—N—O 180° and bent, Ru—N—O 120°. Since NO+ is isoelectronic with CO, linear Ru-N-O bonding is generally treated as coordination of NO+, with bent coordination corresponding to NO- thus, in the former an electron has initially been donated from NO to Ru, as well as the donation of the lone pair, whereas in the latter an electron is donated from the ruthenium to NO (making it NO-) followed by donation of the lone pair from N. Though an oversimplification, this view allows a rationale of metal-nitrogen bond lengths, as with the Ru—NO+ model 7r-donation is important and a shorter Ru-NO bond is predicted - and, in fact, observed. [Pg.43]

Diagnosing the mode of NO coordination, without resort to crystallographic study, can potentially be achieved using the position of i/(N-0) [Pg.43]

The NO ligand can be supplied by nitric oxide itself, but there are many other sources such as nitrite, nitrate or nitric acid, nitrosonium salts or N-methyl-JV-nitrosotoluene-p-sulphonamide (MNTS). The introduction of a nitrosyl group into a ruthenium complex is an ever-present possibility. [Pg.44]

Cases are known where electrophilic attack occurs at nitrite [118] [Pg.45]

Two types of NO coordination to ruthenium are known linear Ru—N-O - 180° and bent, Ru—N—O Since NO is isoelectronic with CO, [Pg.43]

The NO ligand is usually regarded as a good cr-donor and, therefore, electrophilic, so that the above reaction can be reversed by nucleophilic attack [Pg.44]

Complexes of chelating ligands like ethylenediamine (en) and diethylene-triamine (dien) can be made [119]  [Pg.44]

Three isomers of [Ru(NO)Cl (2equ)2] (2equ = 2-ethyl-8-quinolinate) have been isolated in the solid state they interconvert in DMSO solution above 100°C (NMR) [120]. [Pg.44]

Recent study of the [Ru(NO)X5] species (X = halogen, CN) shows that in general the Ru—X bond trans to nitrosyl is slightly longer than the cis-Ru-X bond (Table 1.10) [121]. [Pg.44]

10 higher than for the analogous equilibrium with [Fe(CN)5NO] . This higher affinity of ruthenium-co-ordinated NO for OH is in keeping with its postulation as NO .  [Pg.357]

IR spectroelectrochemistry (vNO) has been used to follow the reaction of Fe(OEP)Cl -I- N02, e.g. formation of Fe(OEP)NO, with vNO at 1672 cm vNO in [Fe(0EP)N0] C104 is dependent on the solvent used for the preparation (1838-1868 cm in the solid state). These differences are ascribed to soHd-state structural differences. Several papers have used IR and/or resonance Raman studies on vNO bands to probe structure and bonding in NO-adducts of biologically important systems.  [Pg.305]

IR spectroelectrochemical studies on Ru2(Fap)4(NO)Cl, where Fap = 2-(2-fluoroanilino)-pyridinate anion, show that NO remains bound in the complex on reduction and that the first reduction adds an electron to the Ru2 core and not to NO. There is IR evidence for Ru-NO/Ru-ON linkage isomerism in the metastable state I of frans-[Ru(NH3)4(NO)(nicotinamide)] +.  [Pg.305]

The IR spectra have been reported for [Ru(N02)4(N0)0H] in the ground state and in a long-lived metastable (MS) state. The ground state vNO of 1914 cm shifts to 1790 cm in the MS state, suggesting the formation of a bent Ru-N-0 unit. IR bands due to vNO have been assigned for [Ru(NO)-(py S4)], where py S4 = 2,6-bis(2-mercapto-3,5-di-tert-butylphenyl)di-thiolate 1841 cm (solid), 1879 cm (methanol solution).  [Pg.305]

Values of vNO were reported for NO adsorbed on NiO-MgO and NiO-CaO surfaces. Adsorption of NO on non-stoichiometric Ni-Cu manganites produces numerous surface species (mono- and dinitrosyls, adsorbed N2O, nitrites and nitrates)  [Pg.306]

Laser-ablated M (= Ga, In or Tl) atoms and NO give trapped products with vNO at 1578.5 cm (Ga), 1524.9 cmr (In) and 1454.6 cm (Tl). Isotopic shifts and DFT calculations show that these are due MNO species.  [Pg.306]


Substituted derivatives of nickelocene, where one ring has been replaced, include the complex cyclopentadienyl nitrosyl nickel [12071 -73-7], (7T-C3H3)NiNO, a red Hquid, mp -41°C. A review of nitrosyl complexes with nickel is available (89). The dimer complex... [Pg.12]

Binary Compounds. The mthenium fluorides are RuF [51621 -05-7] RuF [71500-16-8] tetrameric (RuF ) [14521 -18-7] (15), and RuF [13693-087-8]. The chlorides of mthenium are RUCI2 [13465-51-5] an insoluble RuCl [10049-08-8] which exists in an a- and p-form, mthenium trichloride ttihydrate [13815-94-6], RuCl3-3H2 0, and RuCl [13465-52-6]. Commercial RuCl3-3H2 0 has a variable composition, consisting of a mixture of chloro, 0x0, hydroxo, and often nitrosyl complexes. The overall mthenium oxidation state is closer to +4 than +3. It is a water-soluble source of mthenium, and is used widely as a starting material. Ruthenium forms bromides, RuBr2 [59201-36-4] and RuBr [14014-88-1], and an iodide, Rul [13896-65-6]. [Pg.177]

The coordination chemistry of NO is often compared to that of CO but, whereas carbonyls are frequently prepared by reactions involving CO at high pressures and temperatures, this route is less viable for nitrosyls because of the thermodynamic instability of NO and its propensity to disproportionate or decompose under such conditions (p. 446). Nitrosyl complexes can sometimes be made by transformations involving pre-existing NO complexes, e.g. by ligand replacement, oxidative addition, reductive elimination or condensation reactions (reductive, thermal or photolytic). Typical examples are ... [Pg.448]

Figure 11.13 Structures of polynuclear nitrosyl complexes (a) ((Cr( j -C5H5)(NO))2(M2-NH2)(M2-NO) showing linear-terminal and doubly bridging NO and (b) (Mn3( j -C5H5)3( 3-NO)3( 3-NO)] showing double-and triply-bridging NO the molecule has virtual symmetry and the average Mn-Mn distance is 250 pm (range 247-257 pm). Figure 11.13 Structures of polynuclear nitrosyl complexes (a) ((Cr( j -C5H5)(NO))2(M2-NH2)(M2-NO) showing linear-terminal and doubly bridging NO and (b) (Mn3( j -C5H5)3( 3-NO)3( 3-NO)] showing double-and triply-bridging NO the molecule has virtual symmetry and the average Mn-Mn distance is 250 pm (range 247-257 pm).
This is the second of the common oxidation states for iron and is familiar for ruthenium, particularly with Group 15-donor ligands (Ru probably forms more nitrosyl complexes than any other metal). Osmium(II) also produces a considerable number of complexes but is usually more strongly reducing than Ru". [Pg.1091]

Reaction of [Ir(rj -cod)(/x-pz)]2 with nitrosyl tetrafluoroborate yields 140 (L2 = cod), the cationic nitrosyl complex [85JCS(CC)908]. The 3-methylpyra-zolato complex reveals the same type of behavior, while 3,5-dimethylpyrazolato derivatives give a different kind of product Oxidation of [Ir( j -cod)(/i,-pz )]2 with nitrosyl tetrafluoroborate or hexafluorophosphate leads to 141 (X = BF4, PFg). [Pg.192]

Table 1.9 summarizes structural data for a number of ruthenium nitrosyl complexes, along with IR data [121, 122],... [Pg.44]

Table 1.9 Ruthenium nitrosyl complexes structural and IR data ... Table 1.9 Ruthenium nitrosyl complexes structural and IR data ...
Figure 1.67 Syntheses of some osmium nitrosyl complexes. Figure 1.67 Syntheses of some osmium nitrosyl complexes.
Figure 2.100 Synthesis of some iridium nitrosyl complexes. Figure 2.100 Synthesis of some iridium nitrosyl complexes.
Figure 2.101 Synthesis of some rhodium nitrosyl complexes. Figure 2.101 Synthesis of some rhodium nitrosyl complexes.
Table 2.14 Structural data for iridium nitrosyl complexes... Table 2.14 Structural data for iridium nitrosyl complexes...
Figure 2.102 Addition reactions for iridium nitrosyl complexes (i (N-O) (cm ) is shown for... Figure 2.102 Addition reactions for iridium nitrosyl complexes (i (N-O) (cm ) is shown for...
Monovalent Nitrile complexes Nitrite complexes Nitrosyl complexes NMR spectra... [Pg.390]

Principles of structure, bonding and reactivity for metal nitrosyl complexes. J. H. Enemark and R. D. Feltham, Coord. Chem. Rev., 1974,13, 339-406 (126). [Pg.40]

Carter, O. L., McPhail, A. T. Sim, G. A. (1967) Metal-carbonyl and metal-nitrosyl complexes. Part V. The crystal and molecular structure of the tricarbonylchromium derivative of methyl benzoate, J. Chem. Soc. A, 1619-1626. [Pg.245]


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Addition reactions, transition metal nitrosyl complexes

Azanone nitrosyl complexes

Bond lengths nitrosyl complexes

Catalysts nitrosyl complexes, transition metal

Chromium complexes nitrosyls

Cobalt complex compounds pentaammine nitrosyl

Cobalt complex nitrosyl

Cobalt complexes nitrosyls

Cobalt porphyrins nitrosyl complexes

Cobalt, nitrosyl complexes, reaction with

Cobalt, nitrosyl complexes, reaction with oxygen

Complexes containing nitrosyl or thionitrosyl groups

Complexes containing nitrosyl or thionitrosyl ligands

Coordination number, transition metal nitrosyl complexes

Copper nitrosyl complexes bridging

Copper, nitrosyl complexes

Cyclopentadienyl metal nitrosyl complexes

Cyclopentadienyl nitrosyl complexes

Cytochrome nitrosyl complexes

Examples from the Chemical Biology of Metal Nitrosyl Complexes

Ferritin, nitrosyl complexes

Formation of Metal Nitrosyl Complexes

Heme nitrosyl porphyrinate complexes

Hemoglobin, nitrosyl complexes

Iridium complexes nitrosyls

Iron complexes nitrosyl bonding studies

Iron complexes nitrosyls

Iron porphyrins nitrosyl complexes

Iron-sulfur-nitrosyl complexes

Iron-sulfur-nitrosyl complexes salts

Ligand structures nitrosyl complexes

Manganese complexes carbonyl-nitrosyl

Manganese complexes nitrosyls

Manganese porphyrins nitrosyl complexes

Metal carbonyls reaction with nitrosyl complexes

Metal-nitrogen bonding nitrosyl complexes

Metal-nitrosyl complexes

Metal/metallic nitrosyls complexes

Molybdenum complexes nitrosyl

Molybdenum complexes nitrosyl cyclopentadienyls

Molybdenum complexes nitrosyl sulfur

Molybdenum complexes, with nitrosyl

Myoglobin, nitrosyl complexes

Nickel complexes nitrosyl

Niobium Nitrosyl complexes

Nitric oxide metal nitrosyl complexes

Nitric oxide nitrosyl complexes

Nitric oxide transition metal nitrosyl complexes

Nitrosation with metal nitrosyl complexes

Nitrosyl Complexes (Written with Prof. Jesse W. Tye)

Nitrosyl Complexes of Iron-Sulfur

Nitrosyl and Aryldiazo Complexes

Nitrosyl and Selenonitrosyl Complexes

Nitrosyl and thionitrosyl complexes

Nitrosyl complex catalysts

Nitrosyl complexes MO diagrams

Nitrosyl complexes bent bonds

Nitrosyl complexes bonding

Nitrosyl complexes bridging

Nitrosyl complexes chemistry

Nitrosyl complexes chromium

Nitrosyl complexes coordination modes

Nitrosyl complexes decomposition

Nitrosyl complexes electronic structure

Nitrosyl complexes electrophilic addition

Nitrosyl complexes formation

Nitrosyl complexes halides

Nitrosyl complexes insertion reactions

Nitrosyl complexes iridium

Nitrosyl complexes isomerization

Nitrosyl complexes ligand

Nitrosyl complexes linear

Nitrosyl complexes manganese

Nitrosyl complexes metal hydroxides

Nitrosyl complexes metal-hydride compounds

Nitrosyl complexes molybdenum dithiocarbamates

Nitrosyl complexes mononuclear, bonding

Nitrosyl complexes mononuclear, structure

Nitrosyl complexes nucleophilic addition

Nitrosyl complexes of chromium

Nitrosyl complexes of chromium, molybdenum and

Nitrosyl complexes of chromium, molybdenum, and tungsten

Nitrosyl complexes of iridium

Nitrosyl complexes of iron

Nitrosyl complexes of iron-sulfur clusters

Nitrosyl complexes of molybdenum

Nitrosyl complexes of nickel

Nitrosyl complexes of osmium

Nitrosyl complexes of rhodium

Nitrosyl complexes of ruthenium

Nitrosyl complexes of transition metals

Nitrosyl complexes oxidative processes

Nitrosyl complexes preparation

Nitrosyl complexes reaction with carbon monoxide

Nitrosyl complexes reactivity

Nitrosyl complexes reductive processes

Nitrosyl complexes shift tensor components

Nitrosyl complexes small molecule conversion

Nitrosyl complexes spectroscopy

Nitrosyl complexes square pyramidal

Nitrosyl complexes structures

Nitrosyl complexes syntheses

Nitrosyl complexes technetium

Nitrosyl complexes tungsten

Nitrosyl complexes vibrational spectra

Nitrosyl complexes, electron-transfer reactions

Nitrosyl complexes, osmium

Nitrosyl complexes, review

Nitrosyl cyano complexes

Nitrosyl metal complexes, organometallic

Nitrosyl metal complexes, organometallic bonding

Nitrosyl metal complexes, organometallic structures

Nitrosyl molybdenum silsesquioxane complex

Nitrosyl, and Isocyanide Complexes

Nitrosyl-iron complexes

Nitrosyl-metal complexes Subject

Nitrosylation NO-complexes

Nitrosyls complexes

Nitrosyls complexes

Nitrous nitrosyl complexes

Nonheme iron nitrosyl complexes

Organometallic nitrosyl complexes

Protonation, transition metal nitrosyl complexes

Reactions of Metal Nitrosyl Complexes

Reductive nitrosylation, transition metal nitrosyl complexes

Resonance structures nitrosyl complexes

Rhenium complexes carbonyl nitrosyls

Rhenium complexes nitrosyl

Rhodium complexes nitrosyl

Ruthenium complexes nitrosyl clusters

Ruthenium complexes nitrosyls

Ruthenium nitrosyl complex

Ruthenium nitrosyl complexes nitric oxide

Ruthenium nitrosyl complexes structures

Structural Characterisation of Nitrosyl Complexes

Structural studies metal nitrosyl complexes

Technetium nitrosyl and thionitrosyl complexes

Transition Metal Nitrosyl Complexes D. Michael, P. Mingos, and Darren

Transition Metal Nitrosyl Complexes Sherman

Transition metal nitrosyl complexes

Transition metal nitrosyl complexes characterization

Transition metal nitrosyl complexes energy

Transition metal nitrosyl complexes reactions

Tungsten complexes nitrosyl clusters

Tungsten complexes with nitrosyl

Vanadium complexes nitrosyl

Vanadium complexes nitrosyls

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