Multiplet antiphase

As mentioned already, the INEPT spectra are typified by the antiphase character of the individual multiplets. The INEPT C-NMR spectrum of 1,2-dibromobutane is shown, along with the normal off-resonance C-NMR spectrum, in Fig. 2.12. Doublets show one peak with positive phase and the other with negative phase. Triplets show the outer two peaks with positive and negative amplitudes and the central peak with a weak positive amplitude. Quartets have the first two peaks with positive amplitudes and the remaining two peaks with negative amplitudes. 

The basic INEPT spectrum cannot be recorded with broad-band proton decoupling, since the components of multiplets have antiphase disposition. With an appropriate increase in delay time, the antiphase components of the multiplets appear in phase. In the refocussed INEPT experiment, a suitable refocusing delay is therefore introduced that allows the C spin multiplet components to get back into phase. The pulse sequences and the resulting spectra of podophyllotoxin (Problem 2.21) from the two experiments are given below ... 

Both experiments are based on polarization transfer from sensitive nuclei to insensitive nuclei, and therefore the mjyor portions of their pulse sequences are common. The INEPT experiment, without refocusing and decoupling, however, yields spectra with distorted" multiplets. For instance, the two lines of a doublet appear in antiphase with respect one another. Similarly, the central line of a triplet may be too small to be visible, while the outer two lines of the triplet will be antiphase to one another. Introducing a variable refocusing delay A and broadband decoupling in the INEPT sequence can convert this experiment into a more useful one. 

Since many of the signals in COSY spectra are in antiphase, they may not show up as cross-peaks due to the intrinsic nature of the polarization transfer experiment. The intensities of cross-peaks in COSY spectra may be represented by an antiphase triangle (Fig. 5.33B), in contrast to multiplet... 

One problem associated with COSY spectra is the dispersive character of the diagonal peaks, which can obliterate the cross-peaks lying near the diagonal. Moreover, if the multiplets are resolved incompletely in the crosspeaks, then because of their alternating phases an overlap can weaken their intensity or even cause them to disappear. In double-quantum filtered COSY spectra, both the diagonal and the cross-peaks possess antiphase character, so they can be phased simultaneously to produce pure 2D absorption line... 

A 90° Gaussian pulse is employed as an excitation pulse. In the case of a simple AX spin system, the delay t between the first, soft 90° excitation pulse and the final, hard 90° detection pulse is adjusted to correspond to the coupling constant JJ x (Fig- 7.2). If the excitation frequency corresponds to the chemical shift frequency of nucleus A, then the doublet of nucleus A will disappear and the total transfer of magnetization to nucleus X will produce an antiphase doublet (Fig. 7.3). The antiphase structure of the multiplets can be removed by employing a refocused ID COSY experiment (Hore, 1983). 

The purpose of the C(o i)-half-filter is to start the TOCSY experiment only with the magnetization of protons bound to C. No further C pulses are applied after the start of the evolution time t. For the description of the multiplet fine-structure of the resulting cross-peaks, it is instructive to consider a 3-spin system with the operators H, and C denoting the spins of two protons and one carbon. Starting from antiphase magnetiza-... 

Figures Pt H NMR spectra of [Pt(C5H5 N)(PPh3)Cl2] recorded in THF (bottom) normal spectrum (middle) with INEPT enhancement from P, yijys = 40.48/21.50 2, note the antiphase multiplet (top) with refocused INEPT enhancement from P, note slight loss of intensity due to signal dephasing during the longer pnlse sequence...

For the qualitative and quantitative determination of coupling constants, Hartmann-Hahn transfer can be of assistance and also provides a number of new approaches. These approaches are based on Hartmann-Hahn transfer functions or on the efficient transfer of coherence in one subset of the spin system while the polarization of a second subset of spins remains untouched (E.COSY principle). Furthermore, in combination with other experiments, the in-phase multiplets of Hartmann-Hahn experiments can be used as a reference in an iterative fitting of coupling constants in antiphase multiplets. 

Figure 2.13. Scalar couplings in the rotating frame. Multiplet components evolve according to their coupling constants. The vectors have an antiphase disposition after an evolution period of 1/2J and 1/4J s for doublets and triplets respectively.

Figure 5.43. ID double-quantum filtration of the spectrum of the peptide Leu-enkephalin 5.4 in CD3OD. The singlet resonances of the solvent, truncated in the conventional ID spectrum (a), have been filtered out in (b). The remaining peaks in (b) display the characteristic antiphase multiplet structure (which may be masked by magnitude calculation if desired).

Figure 5.47. (a) The conventional Pascal s triangle for ID multiplets and (b) the antiphase equivalent for predicting COSY multiplet structures from coupling to n equivalent spins. 

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