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1.
Tousek J Van Miert S Pieters L Van Baelen G Hostyn S Maes BU Lemière G Dommisse R Marek R 《Magnetic resonance in chemistry : MRC》2008,46(1):42-51
Indoloquinoline alkaloids represent an important class of antimalarial, antibacterial and antiviral compounds. They have been shown to bind to DNA via intercalation preferentially at GC-rich sequences containing nonalternating CC sites. The stability of complexes formed with biological macromolecules depends on noncovalent binding. In the present study, the ability of indoloquinolines to form intermolecular interactions with solvents was investigated by using NMR spectroscopy and density functional theory (DFT) (B3LYP/6-31G**) calculations. NMR data measured for indoloquinoline bases and the corresponding hydrochlorides are discussed in relation to the structure. DFT calculations of shielding constants in vacuo and in solution allowed the investigation of the influence of the environment on the NMR parameters. Calculations incorporating solvent effects indicated significant changes in the anisotropy of the electron distribution, reflected in the span of the chemical shielding tensor (Omega = sigma11 - sigma33). Solvent effects on the span of the 13C and 15N shielding tensor depended on the type of atom and the data indicated a significant influence of solute-solvent interactions. 相似文献
2.
Lo AY Bitterwolf TE Macdonald CL Schurko RW 《The journal of physical chemistry. A》2005,109(32):7073-7087
Solid-state 93Nb and 13C NMR experiments, in combination with theoretical calculations of NMR tensors, and single-crystal and powder X-ray diffraction experiments, are applied for the comprehensive characterization of structure and dynamics in a series of organometallic niobium complexes. Half-sandwich niobium metallocenes of the forms Cp'Nb(I)(CO)4 and CpNb(V)Cl4 are investigated, where Cp = C5H5- and Cp' = C5H4R- with R = COMe, CO2Me, CO2Et, and COCH2Ph. Anisotropic quadrupolar and chemical shielding (CS) parameters are extracted from 93Nb MAS and static NMR spectra for seven different complexes. It is demonstrated that 93Nb NMR parameters are sensitive to changes in temperature and Cp' ring substitution in the Cp'Nb(I)(CO)4 complexes. There are dramatic differences in the 93Nb quadrupolar coupling constants (C(Q)) between the Nb(I) and Nb(V) complexes, with C(Q) between 1.0 and 12.0 MHz for Cp'Nb(CO)4 and C(Q) = 54.5 MHz for CpNbCl4. The quadrupolar Carr-Purcell Meiboom-Gill (QCPMG) pulse sequence is applied to rapidly acquire, in a piecewise fashion, a high signal-to-noise ultra-wide-line 93Nb NMR spectrum of CpNbCl4, which has a breadth of ca. 400 kHz. Solid-state 93Nb and 13C NMR spectra and powder XRD data are used to identify a new metallocene adduct coordinated at the axial position of the metal site by a THF molecule: CpNb(V)Cl4.THF. 13C MAS and CP/MAS NMR experiments are used to assess the purity of samples, as well as for measuring carbon CS tensors and the rare instance of one-bond 93Nb, 13C J-coupling, 1J(93Nb,13C). Theoretically calculated CS and electric field gradient (EFG) tensors are utilized to determine relationships between tensor orientations, the principal components, and molecular structures. 相似文献
3.
Platinum(IV) halides formed complexes of the type PtL2X4 [L=1-vinyl imidazole (1,-VIm), 1-methylimidazole (1-MeIm), 1,2-dimethylimidazole (1,2-Me2Im), 1-vinyl-2-methylimidazole (1-V-2-MeIm), 2-methylimidazole (2-MeIm), 2-ethylimidazole (2-EtIm), 2-isopropylimidazole (2-i-PrIm), and 4-methylimidazole (4-MeIm); X=Cl, Br] in neutral aqueous solution. The 1-n-butylimidazole (1-n-BuIm) ligand yielded only (LH)2PtX6 compound in the same medium. The compounds were characterised by elemental analyses, IR, UV-VIS and 1HNMR spectra. 相似文献
4.
A series of low-spin six-coordinate (tetraphenylchlorinato)iron(III) complexes [Fe(TPC)(L)2]+/- (L = 1-MeIm, CN-, 4-CNPy, and (t)BuNC) have been prepared, and their (13)C NMR spectra have been examined to reveal the electronic structure. These complexes exist as the mixture of the two isomers with the (d(xy))2(d(xz), d(yz))3 and (d(xz), d(yz))4(d(xy))1 ground states. Contribution of the (d(xz), d(yz))4(d(xy))1 isomer has increased as the axial ligand changes from 1-MeIm, to CN(-) (in CD2Cl2 solution), CN- (in CD(3)OD solution), and 4-CNPy, and then to tBuNC as revealed by the meso and pyrroline carbon chemical shifts; the meso carbon signals at 146 and -19 ppm in [Fe(TPC)(1-MeIm)2]+ shifted to 763 and 700 ppm in [Fe(TPC)(tBuNC)2]+. In the case of the CN- complex, the population of the (d(xz), d(yz))4(d(xy))1 isomer has increased to a great extent when the solvent is changed from CD2Cl2 to CD3OD. The result is ascribed to the stabilization of the d(xz) and d(yz) orbitals of iron(III) caused by the hydrogen bonding between methanol and the coordinated cyanide ligand. Comparison of the 13C NMR data of the TPC complexes with those of the TPP, OEP, and OEC complexes has revealed that the populations of the (d(xz), d(yz))4(d(xy))1 isomer in TPC complexes are much larger than those in the corresponding TPP, OEC, and OEP complexes carrying the same axial ligands. 相似文献
5.
The determination of backbone conformations in powdered peptides using 13C and 15N shift tensor information is explored. The 13C and 15N principal shift values in natural abundance 13C and 15N melanostatin (L-Pro-L-Leu-Gly amide) are measured using the FIREMAT technique. Furthermore, the orientation of the C-N bond in the 13C shift principal axis system for the backbone carbons is obtained from the presence of the 13C-14N dipolar coupling. The Ramachandran angles for the title compound are obtained from solid-state NMR data by comparing the experimentally determined shift tensor information to systematic theoretical shielding calculations on N-formyl-L-amino acid-amide models. The effects of geometry optimization and neglect of intermolecular interactions on the theoretical shielding values in the model compounds are investigated. The sets of NMR derived Ramachandran angles are assembled in a set of test structures that are compared to the available single-crystal X-ray structure. Shift tensor calculations on the test structures and the X-ray structure are used to further assess the importance of intermolecular interactions when the shift tensor is used as a structural probe in powdered peptides. 相似文献
6.
Silvernail NJ Roth A Schulz CE Noll BC Scheidt WR 《Journal of the American Chemical Society》2005,127(41):14422-14433
The synthesis and characterization of four low-spin (carbonyl)iron(II) tetraphenylporphyrinates, [Fe(TPP)(CO)(L)], where L = 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole (unsolvated), and 1,2-dimethylimidazole (toluene solvate) are reported. The complexes show nearly the same value of nu(C-O) in toluene solution (1969-72 cm(-1)) but a large range of CO stretching frequencies in the solid-state (1926-1968 cm(-1)). The large solid-state variation results from CO interactions in the solid state, as shown by an examination of the crystal structures of the four complexes. The high precision of the four structures obtained allows us to make a number of structural and spectroscopic correlations that describe the Fe-C-O and N(Im)-Fe-CO units. The values of nu(C-O) and the Fe-C and C-O bond distances are strongly correlated and provide a structural, as well as a spectroscopic, correlation of the pi back-bonding model. The interactions of CO described are closely related to the large range of CO stretching frequencies observed in heme proteins and specific interactions observed in carbonylmyoglobin (MbCO). 相似文献
7.
The (13)C and (15)N chemical shift tensor principal values for adenosine, guanosine dihydrate, 2'-deoxythymidine, and cytidine are measured on natural abundance samples. Additionally, the (13)C and (15)N chemical shielding tensor principal values in these four nucleosides are calculated utilizing various theoretical approaches. Embedded ion method (EIM) calculations improve significantly the precision with which the experimental principal values are reproduced over calculations on the corresponding isolated molecules with proton-optimized geometries. The (13)C and (15)N chemical shift tensor orientations are reliably assigned in the molecular frames of the nucleosides based upon chemical shielding tensor calculations employing the EIM. The differences between principal values obtained in EIM calculations and in calculations on isolated molecules with proton positions optimized inside a point charge array are used to estimate the contributions to chemical shielding arising from intermolecular interactions. Moreover, the (13)C and (15)N chemical shift tensor orientations and principal values correlate with the molecular structure and the crystallographic environment for the nucleosides and agree with data obtained previously for related compounds. The effects of variations in certain EIM parameters on the accuracy of the shielding tensor calculations are investigated. 相似文献
8.
Hu B Hauksson JB Tran AT Kolczak U Pandey RK Rezzano IN Smith KM La Mar GN 《Journal of the American Chemical Society》2001,123(41):10063-10070
The 1H and 13C chemical shifts for the heme methyls of low-spin, ferric sperm whale cyanometmyoglobin reconstituted with a variety of centrosymmetric and pseudocentrosymmetric hemins have been recorded and analyzed to shed light on the nature of heme-protein contacts, other than that of the axial His, that modulate the rhombic perturbation to the heme's in-plane electronic asymmetry. The very similar 1H dipolar shifts for heme pocket residues in all complexes yield essentially the same magnetic axes as in wild type, and the resultant dipolar shifts allow the direct determination of the heme methyl proton and 13C contact shifts in all complexes. It is demonstrated that, even when the magnetic axes and anisotropies are known, the intrinsic uncertainties in the orientational parameters lead to a sufficiently large uncertainty in dipolar shift that the methyl proton contact shifts are inherently significantly less reliable indicators of the unpaired electron spin distribution than the methyl 13C contact shifts. The pattern of the noninversion symmetry in 13C contact shifts in the centro- or pseudocentrosymmetric hemes is shown to correlate with the positions of aromatic rings of Phe43(CD1) and His97(FG3) parallel to, and in contact with, the heme. These results indicate that such pi-pi interactions significantly perturb the in-plane asymmetry of the heme pi spin distribution and cannot be ignored in a quantitative interpretation of the heme methyl 13C contact shifts in terms of the axial His orientation in b-type hemoproteins. 相似文献
9.
HOU Guangjin WANG Liying LU Xiaoming ZHENG Anmin DENG Feng &YE Chaohui . Department of Physics Huazhong University of Science Technology Wuhan China . State Key Laboratory of Magnetic Resonance Atomic Molecular Physics Wuhan Institute of Physics Mathematics Chi-nese Academy of Sciences Wuhan China . Department of Chemistry Capital Normal University Beijing China 《中国科学B辑(英文版)》2004,47(3)
~~Experimental and theoretical study of~(13)C shielding tensors in new-style molybdenum complex~~ 相似文献
10.
Parameterization of peptide 13C carbonyl chemical shielding anisotropy in molecular dynamics simulations. 总被引:1,自引:0,他引:1
Daniel M Jordan K Maria Mills Ioan Andricioaei Akash Bhattacharya Kim Palmo Erik R P Zuiderweg 《Chemphyschem》2007,8(9):1375-1385
NMR chemical shielding anisotropy (CSA) relaxation is an important tool in the study of dynamical processes in proteins and nucleic acids in solution. Herein, we investigate how dynamical variations in local geometry affect the chemical shielding anisotropy relaxation of the carbonyl carbon nucleus, using the following protocol: 1) Using density functional theory, the carbonyl (13)C' CSA is computed for 103 conformations of the model peptide group N-methylacetamide (NMA). 2) The variations in computed (13)C' CSA parameters are fitted against quadratic hypersurfaces containing cross terms between the variables. 3) The predictive quality of the CSA hypersurfaces is validated by comparing the predicted and de novo calculated (13)C' CSAs for 20 molecular dynamics snapshots. 4) The CSA fluctuations and their autocorrelation and cross correlation functions due to bond-length and bond-angle distortions are predicted for a chemistry Harvard molecular mechanics (CHARMM) molecular dynamics trajectory of Ca(2+)-saturated calmodulin and GB3 from the hypersurfaces, as well as for a molecular dynamics (MD) simulation of an NMA trimer using a quantum mechanically correct forcefield. We find that the fluctuations can be represented by a 0.93 scaling factor of the CSA tensor for both R(1) and R(2) relaxations for residues in helix, coil, and sheet alike. This result is important, as it establishes that (13)C' relaxation is a valid tool for measurement of interesting dynamical events in proteins. 相似文献
11.
Carbon-13 chemical shift anisotropy (CSA) tensors for various carbon sites of polypeptides, and for carbon sites in alpha-helical and beta-sheet conformations of poly-L-alanine, and polyglycine, are presented. The carbonyl (13)C CSA tensors were determined from one-dimensional CPMAS spectra obtained at a slow spinning speed, whereas the CSA tensors of C(alpha) and other carbons in side chains of peptides were determined using 2D PASS experiments on powder samples. The results suggest that the spans of (13)Carbonyl CSA tensors of alanine and glycine residues in various peptides are similar, even though the magnitude of individual components of the CSA tensor and the isotropic chemical shift are different. In addition, the delta(22) element is the only component of the (13)Carbonyl CSA tensor that significantly depends on the CO.HN hydrogen-bond length. Solid-state NMR experimental results also suggest that (13)Carbonyl and (13)C(alpha) CSA tensors are similar for alpha-helical and beta-sheet conformations of poly-L-alanine, which is in agreement with the reported quantum chemical calculation studies and previous solid-state NMR experimental studies on other systems. On the other hand, the (13)C(alpha) CSA tensor of the first alanine residue is entirely different from that of the second or later alanine residues of the peptide. While no clear trends in terms of the span and the anisotropic parameter were predicted for (13)C(beta) CSA tensors of alanine, they mainly depend on the conformation and dynamics of the side chain as well as on the packing interactions in the solid state of peptides. 相似文献
12.
Chekmenev EY Xu RZ Mashuta MS Wittebort RJ 《Journal of the American Chemical Society》2002,124(40):11894-11899
We report here (13)C(alpha) chemical shielding parameters for central Gly residues in tripeptides adopting alpha-helix, beta-strand, polyglycine II, and fully extended 2 degrees structures. To assess experimental uncertainties in the shielding parameters and the effects of (14)N-(13)C(alpha) or (15)N-(13)C(alpha) dipolar coupling, stationary and magic angle spinning (MAS) spectra with and without (15)N decoupling were obtained from natural abundance and double-labeled samples containing [2-(13)C, (15)N]Gly. We find that accurate (<1 ppm uncertainty) shielding parameters are measured with good sensitivity and resolution in (15)N decoupled 1D or 2D MAS spectra of double-labeled samples. Compared to variations of isotropic shifts with peptide angles, those of (13)C(alpha) shielding anisotropy and asymmetry are greater. Trends relating shielding parameters to the 2 degrees structure are apparent, and the correlation of the experimental values with unscaled ab initio shielding calculations has an rms error of 3 ppm. Using the experimental data and the ab initio shielding values, the empirical trends relating the 2 degrees structure to shielding are extended to the larger range of torsion angles found in proteins. 相似文献
13.
13C NMR relaxation times T(1) of the carbonyl groups of pentane-2,4-dione and beta-diketonate complexes Al(acac)(3) and Zr(acac)(4) (acac: pentanedionate anion) were measured for various magnetic field strengths, allowing a determination of the contribution of the chemical shift anisotropy mechanism to the total relaxation. NOE and T(1) measurements for the (13)C nucleus of the central methine carbon furnished the correlation time tau(c) for the reorientation of theses species. The chemical shift tensor anisotropy Deltasigma could be deduced and compared to the values obtained in the solid state. The quadrupolar coupling constant (QCC) of the (17)O nucleus could also be determined by measuring the line width of the (17)O NMR signal and using the tau(c) value. QCC values for the complexes are in the same range as for the pentane-2,4-dione molecule, indicating similar electronic distribution and symmetry around the oxygen atom of these different species. Deltasigma for the complexes are close together, and the values obtained in solution are approximately those obtained in the solid state. They are close to the value reported in the literature for tetraacetylethane, which can be considered as a dimer of a beta-diketone, but slight differences are observed for the individual components of the chemical shielding tensor. 相似文献
14.
We have used ab initio quantum chemical techniques to compute the (13)C(alpha) and (13)C(beta) shielding surfaces for the 14 amino acids not previously investigated (R. H. Havlin et al., J. Am. Chem. Soc. 1997, 119, 11951-11958) in their most popular conformations. The spans (Omega = sigma(33) - sigma(11)) of all the tensors reported here are large ( approximately 34 ppm) and there are only very minor differences between helical and sheet residues. This is in contrast to the previous report in which Val, Ile and Thr were reported to have large ( approximately 12 ppm) differences in Omega between helical and sheet geometries. Apparently, only the beta-branched (beta-disubstituted) amino acids have such large CSA span (Omega) differences; however, there are uniformly large differences in the solution-NMR-determined CSA (Deltasigma = sigma(orth) - sigma(par)) between helices and sheets in all amino acids considered. This effect is overwhelmingly due to a change in shielding tensor orientation. With the aid of such shielding tensor orientation information, we computed Deltasigma values for all of the amino acids in calmodulin/M13 and ubiquitin. For ubiquitin, we find only a 2.7 ppm rmsd between theory and experiment for Deltasigma over an approximately 45 ppm range, a 0.96 slope, and an R(2) = 0.94 value when using an average solution NMR structure. We also report C(beta) shielding tensor results for these same amino acids, which reflect the small isotropic chemical shift differences seen experimentally, together with similar C(beta) shielding tensor magnitudes and orientations. In addition, we describe the results of calculations of C(alpha), C(beta), C(gamma)1, C(gamma)2, and C(delta) shifts in the two isoleucine residues in bovine pancreatic trypsin inhibitor and the four isoleucines in a cytochrome c and demonstrate that the side chain chemical shifts are strongly influenced by chi(2) torsion angle effects. There is very good agreement between theory and experiment using either X-ray or average solution NMR structures. Overall, these results show that both C(alpha) backbone chemical shift anisotropy results as well as backbone and side chain (13)C isotropic shifts can now be predicted with good accuracy by using quantum chemical methods, which should facilitate solution structure determination/refinement using such shielding tensor surface information. 相似文献
15.
A number of mono(imidazole)-ligated complexes of perchloro(meso-tetramesitylporphyrinato)iron(III), [Fe(TMP)L]ClO(4), have been prepared, and their spin states have been examined by (1)H NMR, (13)C NMR, and EPR spectroscopy as well as solution magnetic moments. All the complexes examined have shown a quantum mechanical spin admixed state of high and intermediate-spin (S = 5/2 and 3/2) states though the contribution of the S = 3/2 state varies depending on the nature of axial ligands. While the complex with extremely bulky 2-tert-butylimidazole (2-(t)()BuIm) has exhibited an essentially pure S = 5/2 state, the complex with electron-deficient 4,5-dichloroimidazole (4,5-Cl(2)Im) adopts an S = 3/2 state with 30% of the S = 5/2 spin admixture. On the basis of the (1)H and (13)C NMR results, we have concluded that the S = 3/2 contribution at ambient temperature increases according to the following order: 2-(t)BuIm < 2-(1-EtPr)Im < 2-MeIm 相似文献
16.
We report the experimental determination of the (13)C(alpha) chemical shift tensors of Ala, Leu, Val, Phe, and Met in a number of polycrystalline peptides with known X-ray or de novo solid-state NMR structures. The 700 Hz dipolar coupling between (13)C(alpha) and its directly bonded (14)N permits extraction of both the magnitude and the orientation of the shielding tensor with respect to the C(alpha)-N bond vector. The chemical shift anisotropy (CSA) is recoupled under magic-angle spinning using the SUPER technique (Liu et al., J. Magn. Reson. 2002, 155, 15-28) to yield quasi-static chemical shift powder patterns. The tensor orientation is extracted from the (13)C-(14)N dipolar modulation of the powder line shapes. The magnitudes and orientations of the experimental (13)C(alpha) chemical shift tensors are found to be in good accord with those predicted from quantum chemical calculations. Using these principal values and orientations, supplemented with previously measured tensor orientations from (13)C-(15)N and (13)C-(1)H dipolar experiments, we are able to predict the (phi, psi, chi(1)) angles of Ala and Val within 5.8 degrees of the crystallographic values. This opens up a route to accurate determination of torsion angles in proteins based on shielding tensor magnitude and orientation information using labeled compounds, as well as the structure elucidation of noncrystalline organic compounds using natural abundance (13)C NMR techniques. 相似文献
17.
Knowledge of (13)C chemical shift anisotropy (CSA) in nucleotide bases is important for the interpretation of solution-state NMR relaxation data in terms of local dynamic properties of DNA and RNA. Accurate knowledge of the CSA becomes particularly important at high magnetic fields, prerequisite for adequate spectral resolution in larger oligonucleotides. Measurement of (13)C relaxation rates of protonated carbons in the bases of the so-called Dickerson dodecamer, d(CGCGAATTCGCG)(2), at 500 and 800 MHz (1)H frequency, together with the previously characterized structure and diffusion tensor yields CSA values for C5 in C, C6 in C and T, C8 in A and G, and C2 in A that are closest to values previously reported on the basis of solid-state FIREMAT NMR measurements, and mostly larger than values obtained by in vacuo DFT calculations. Owing to the noncollinearity of dipolar and CSA interactions, interpretation of the NMR relaxation rates is particularly sensitive to anisotropy of rotational diffusion, and use of isotropic diffusion models can result in considerable errors. 相似文献
18.
《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》1992,48(11-12):1589-1599
We report the concentration-dependent resonance Raman (RR) studies of the FENIm stretching modes in the photo-reduced iron-octaethyl porphyrin (FeIIOEP) and iron-protoporphyrin-IX dimethylester (FeIIPPDME) complexes with 2-methyl imidazole (2-MeIm) and 1,2-dimethyl imidazole (1,2-Me2Im) as axial ligands. The FeNIm stretching modes in both iron complexes have revealed two components due to the co-existence of the upright and tilted configurations of the FENIm bond with respect to the normal to the heme plane. The frequencies of the two components in both the complexes shift to higher side with an increase in concentration of 2-MeIm as axial ligand. With the more sterically hindered 1,2-Me2Im as axial ligand, the (1,2-Me2Im)FeII-OEP complex exists mainly with the tilted configuration of the FENIm bond while the upright configuration is the dominant species in the (1,2-Me2Im)FeIIPPDME complex. From the comparative study, we infer that the vinyl groups in the protoporphyrin complex play a dominant role in non-bonded interactions with the sterically hindered axial ligands in stabilizing the specific configurations. 相似文献
19.
7Li and 13C solid-state MAS NMR spectra of three lithium cuprates with known X-ray structures--lithium([12]crown-4)2 dimethyl and diphenyl cuprate (1,2) and lithium(thf)4-[tris(trimethylsilyl) methyl]2 cuprate (3)--have been measured and analysed with respect to the quadrupolar coupling constants of lithium-7, chi(7Li), and the asymmetry parameters of the quadrupolar interactions, eta(7Li), as well as the 6, 7Li and 13C chemical shifts. The chi(7Li) values of 23, 30, and 18 kHz for 1, 2 and 3, respectively, are in line with the high symmetry around the lithium nucleus in the solvent-separated structures and may be used as reference data for this structural motif. Calculations based on charges derived from ab initio 6-31 G* HF computations using the point charge model (PCM) and the program GAMESS support the experimental findings. 相似文献
20.
del Rosal I Maron L Poteau R Jolibois F 《Dalton transactions (Cambridge, England : 2003)》2008,(30):3959-3970
Transition metal hydrides are of great interest in chemistry because of their reactivity and their potential use as catalysts for hydrogenation. Among other available techniques, structural properties in transition metal (TM) complexes are often probed by NMR spectroscopy. In this paper we will show that it is possible to establish a viable methodological strategy in the context of density functional theory, that allows the determination of 1H NMR chemical shifts of hydride ligands attached to transition metal atoms in mononuclear systems and clusters with good accuracy with respect to experiment. 13C chemical shifts have also been considered in some cases. We have studied mononuclear ruthenium complexes such as Ru(L)(H)(dppm)2 with L = H or Cl, cationic complex [Ru(H)(H2O)(dppm)2]+ and Ru(H)2(dppm)(PPh3)2, in which hydride ligands are characterized by a negative 1H NMR chemical shift. For these complexes all calculations are in relatively good agreement compared to experimental data with errors not exceeding 20% except for the hydrogen atom in Ru(H)2(dppm)(PPh3)2. For this last complex, the relative error increases to 30%, probably owing to the necessity to take into account dynamical effects of phenyl groups. Carbonyl ligands are often encountered in coordination chemistry. Specific issues arise when calculating 1H or 13C NMR chemical shifts in TM carbonyl complexes. Indeed, while errors of 10 to 20% with respect to experiment are often considered good in the framework of density functional theory, this difference in the case of mononuclear carbonyl complexes culminates to 80%: results obtained with all-electron calculations are overall in very satisfactory agreement with experiment, the error in this case does not exceed 11% contrary to effective core potentials (ECPs) calculations which yield errors always larger than 20%. We conclude that for carbonyl groups the use of ECPs is not recommended, although their use could save time for very large systems, for instance in cluster chemistry. The reliance of NMR chemical shielding on dynamical effects, such as intramolecular rearrangements or trigonal twists, is also examined for H2Fe(CO)4, K+[HFe(CO)](-), HMn(CO)5 and HRe(CO)5. The accuracy of the theory is also examined for complexes with two dihydrogen ligands (Tp*RuH(H2)2 and [FeH(H2)(DMPE)2]+) and a ruthenium cluster, [H3Ru4(C6H6)4(CO)]+. It is shown that for all complexes studied in this work, the effect of the ligands on the chemical shielding of hydrogen coordinated to metal is suitably calculated, thus yielding a very good correlation between experimental chemical shifts and theoretical chemical shielding. 相似文献