Central transition

This perturbation can cause the non-central transitions (i.e. to be shifted (figure B 1,12,1(b))... 

Fortunately, for non-integer quadnipolar nuclei for the central transition = 0 and the dominant perturbation is second order only (equation Bl.12.8) which gives a characteristic lineshape (figure B1.12.1(cB for axial synnnetry) ... 

Figure Bl.12.8. MAS NMR lineshapes from the central transition lineshape for non-integer quadnipole lineshapes with various (A = / /+l) - 3/4 ...

Advantages. The experiment can be carried out with a conventional fast-spuming MAS probe so that it is straightforward to implement. For recording the satellite transition lineshapes it offers better signal-to-noise and is less susceptible to deadtime effects than static measurements. As the effects differ for each value, a single satellite transition experiment is effectively the same as carrying out multiple field experiments on the central transition. 

The splitting of the d orbital energy levels when ligands are bonded to a central transition atom or ion has already been mentioned (p. 60). Consider the two ions [Co(NH3)g] and [Co(NH3)g] we have just discussed. The splitting of the d orbital energy levels for these two ions is shown in Figure 13.2. 

Electric dipole moment measurements on R3SiCo(CO)4, (R3Si)2Fe(CO)4, and related compounds have indicated a relationship between v(CO) and charge transfer in the Si—M bond within a given series the central transition metal is apparently not charged 156). Application of the relationship to HjSiCo(CO)4 suggests a small bond dipole in the sense... 

JLLS and nRAPT = 200), followed by selective excitation of the central transition, the evolution... 

In all these complexes the cyclopropenone ligand was shown to interact with the central transition element by means of the carbonyl function from spectroscopic criteria, its donor capacity was compared to pyridine-N-oxide282). 

Significant progress in signal enhancement methods for the central transition has been achieved by the implementation of double frequency sweeps (DFS) [62]. The basic idea of DFS, applicable for both static and MAS experiments, is to invert simultaneously the STs so that the populations of the outer spin levels are transferred to the CT energy levels before they are selectively excited (Fig. 4). 

Furthermore, according to (4.9a) the total number of covalent M—L bonds (n + m, both oml and 7TMl) is 10 — k. Because main-group ligands generally are more electronegative than the central transition-metal atom, each such covalent M—L bond can be termed a formal one-electron oxidation of M. The duodectet-rule-conforming oxidation number ( ox) of M is therefore... 

The density of states for a transition state depends upon the non-fixed energy minus the critical energy. Taking the critical energy for the central transition state as an adjustable parameter, we can calculate efficiencies until we find a match with experiment. We have already demonstrated that our calculations for the decomposition transition state (k ), using... 

Al MAS NMR has been demonstrated to be an invaluable tool for the zeoHte sdentist It provides a simple and direct way to quantify the proportions of A1 in four [Al(4)j, five [Al(5)j and six [Al(6)j coordinations. Quantitative determination of these species is an important issue in catalysis, and major effort is devoted on this topic. As mentioned already, for A1 only the central transition (-i-half to —half selective exdtation ) is detected. The central transition is unaffected by first order quadmpolar interaction, but the presence of second order effects causes broadening and complicates the quantitation of the A1 species. Usually hydrated samples and short radiofrequency pulses are employed for quantitative determination of framework and extra framework aluminum species. It is uncertain whether hydration changes the coordination of A1 species. Certain extra framework A1 can have very large quadmpolar interactions resulting in very broad lines ( NMR invisible ) [155, 202]. Unlike Si NMR, Al has a short relaxation time due to its quadmpolar nature, and the Al NMR spectrum with good signal to noise can be obtained in a relatively short time. 

FIGURE 5. Reduction in linewidth in the Li solid state NMR spectrum of the dimer of ( )-2-lithio-l-phenyl-1-(o-hthiophenyl)pent-l-ene (90% Li) by various techniques (a) static Li H spectmm, halfwidth 6.3 kHz (b) Li H CP/MAS spectmm, rotational frequency 3 kHz (c) central transition in the Li H CP/MAS spectmm, halfwidth 130 Hz (d) central transition in the Li H CP/MAS spectmm with additional Li decouphng. The two Li resonances are separated by 1.25 ppm hneshape analysis yields half-widths of 92 and 81 Hz, respectively ... 

In many cases the temperature dependence of the quadrupolar coupling constant is an indicator of dynamic processes, because the symmetry around the lithium cation is affected by motions which are fast on the NMR time scale. If the rate of these processes exceeds 1/x, the effective symmetry around the lithium cation increases and a decrease in x( Li) results. In Li MAS spectra, a broadening of the satellite transitions can be observed which eventually disappear completely if the rate of the dynamic process comes in the order of the quadrupole frequency. This behaviour was observed for the THF solvated dimer of bis(trimethylsilylamido)lithium, where the Li MAS spectrum at 353 K shows only the central transition and the sidebands caused by CSA and homonuclear Li- Li dipole coupling (Figure 27) . The simulation of the high-temperature spectrum yielded —20 ppm and 1300 Hz for these quantities, respectively. The dipole coupling agrees closely with the theoretical value of 1319 Hz calculated from the Li-Li distance of 2.4 A, which was determined by an X-ray study. 

Fig. 6 (Color online) Ti magnetization decay for a the central transition and b the satellite background in BaTiOs allowing for a determination of T2 at T = 430 K > Tc. T2s values were obtained by fitting the experimental points to the theoretical model...

The quadrupole perturbed NMR spectriun of Rb (I = 312) consists of the central hne and two satelUte Unes. In D-RADP-x the nuclear quadrupole couphng constant decreases linearly with x from 9.6 MHz (x = 0) to 6.6 MHz (x = 0.95) [10], whereas the Larmor frequency amounts to 98.163 MHz in a Bo field of 7 T. Due to the substitutional disorder, and the corresponding loss of the translational invariance, the satelHte transitions are inhomogeneously broadened that much, that only the central transition can be directly observed. The position of the corresponding resonance line can be calculated using standard NMR-NQR theory [16], where the second order shift is given by ... 

Accurate measurements of the frequency-resolved transverse spin relaxation T2) of Rb NMR on single crystals of D-RADP-x (x = 0.20, 0.25, 0.30, 0.35) have been performed in a Bq field of 7 Tesla as a function of temperature. The probe head was placed in a He gas-flow cryostat with a temperature stability of 0.1 K. To obtain the spin echo of the Rb - 1/2 -o-+ 1/2 central transition we have used the standard (90 - fi - 180y -ti echo - (2) pulse sequence with an appropriate phase-cycling scheme to ehminate quadrature detection errors and unwanted coherences due to pulse imperfections. To avoid sparking in the He gas, the RF-field Bi had to be reduced to a level where the 7T/2-pulse length T90 equalled 3.5 ps at room temperature. 

Polymerization of cycloalkenes through the double bond without ring opening occurs when initiators other than the ROMP initiators are used, including initiators based on various early transition (Ti, Zr, Hf, V), late transition (Pd, Ni), central transition (Cr, Co), and rare-earth (Ln) metals [Janiak and Lassahn, 2001]. This mode of polymerization is discussed in Secs. 8-lf and 8-6a. 

This consideration also applies to 8-vertex clusters with interstitial atoms. The most spherical 8-vertex deltahedron, namely the bisdisphenoid (Eig. 1), appears to have too small a cavity for an interstitial transition metal. Plowever, the square antiprism has two fewer edges and can be partially flattened to make a puckered eight-membered ring, which can accommodate a transition metal in the center (Pig. 8). Known clusters of this type include M E8" (M = Cr [98], Mo [98], Nb [99] E = As, Sb n = 2,3 for Cr and Mo = 3 for Nb). The transition metal in such structures can be considered to be eight-coordinate with flattened square antiprismatic coordination. The Eg ring (E = As, Sb) can be considered formally to be an octaanion, isoelectronic with the common form of elemental sulfur, Sg. Thus in M Eg (M = Cr, Mo E = As, Sb), the central transition metal has the formal oxidation state of +6. Similarly in Nb Eg , the central niobium atom has its d formal oxidation state of +5. 

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