Radical CIDNP

This section is subdivided according to the molecularity of the process (es) examined. Strictly speaking, no absolute rates are known for any acyloxyl radical CIDNP measurements, included in Section 8.2.1 approach this goal even if they do involve time related assumptions. 

As we saw in Sections 5.2 and 5.3, butadiene and allene react with a variety of hydrides by 1,2 insertion, but butadienes also react with HMn(CO)j to give an apparent 1,4 insertion. Since this 18e hydride has no vacant site and CO dissociation is slow, an indirect mechanism must be operating this is thought to be H atom transfer to give a 1,1-dimethyIallyl radical that is subsequently trapped by the metal (Eq. 7.31). Only substrates that form especially stable radicals can react (e.g., 1,3-diene allyl radical) CIDNP effects can be seen in such... 

CIDNP involves the observation of diamagnetic products fonned from chemical reactions which have radical intemiediates. We first define the geminate radical pair (RP) as the two molecules which are bom in a radical reaction with a well defined phase relation (singlet or triplet) between their spins. Because the spin physics of the radical pair are a fiindamental part of any description of the origins of CIDNP, it is instmctive to begin with a discussion of the radical-pair spin Hamiltonian. The Hamiltonian can be used in conjunction with an appropriate basis set to obtain the energetics and populations of the RP spin states. A suitable Hamiltonian for a radical pair consisting of radicals 1 and 2 is shown in equation (B1.16.1) below [12]. 

Figure Bl.16.4. Part A is the vector representations of the. S state, an intennediate state, and the Jq state of a radical pair. Part B is the radical reaction scheme for CIDNP.

A general reaction scheme for CIDNP is shown in llgnre B1.16.4B. where the radical dynamics in each region... 

Figure Bl.16.5. An example of the CIDNP net effect for a radical pair with one hyperfme interaction. Initial conditions g > g2, negative and the RP is initially singlet. Polarized nuclear spin states and schematic NMR spectra are shown for the recombination and scavenging products in the boxes.

Figure Bl.16.8. Example of CIDNP multiplet effect for a syimnetric radical pair with two hyperfme interactions on each radical. Part A is the radical pair. Part B shows the spin levels with relative Q values indicated on each level. Part C shows the spm levels with relative populations indicated by the thickness of each level and the schematic NMR spectrum of the recombination product.

Roth et aJ [10] have used CIDNP to study the structures of vinylcyclopropane radical cations fomied from precursors such as sabinene (1). 

The radical cation of 1 (T ) is produced by a photo-induced electron transfer reaction with an excited electron acceptor, chloranil. The major product observed in the CIDNP spectrum is the regenerated electron donor, 1. The parameters for Kaptein s net effect rule in this case are that the RP is from a triplet precursor (p. is +), the recombination product is that which is under consideration (e is +) and Ag is negative. This leaves the sign of the hyperfine coupling constant as the only unknown in the expression for the polarization phase. Roth et aJ [10] used the phase and intensity of each signal to detemiine the relative signs and magnitudes of the... 

DH has only one non-negligible hyperfme, = -1-19.0 G while D has two significant hyperfmes, = -13.96 G and = -1-19.24 G. Clearly, these two radicals will lead to very different polarizations in the CIDNP spectmm of both cage and escape products. 

Figure B 1.16.9 shows background-free, pseudo-steady-state CIDNP spectra of the photoreaction of triethylamine with (a) anthroquinone as sensitizer and (b) and (c) xanthone as sensitizer. Details of the pseudo-steady-state CIDNP method are given elsewhere [22]. In trace (a), no signals from the p protons of products 1 (recombination) or 2 (escape) are observed, indicating that the products observed result from the radical ion pair. Traces (b) and (c) illustrate a usefiil feature of pulsed CIDNP net and multiplet effects may be separated on the basis of their radiofrequency (RF) pulse tip angle dependence [21]. Net effects are shown in trace (b) while multiplet effects can...

Wliile the earliest TR-CIDNP work focused on radical pairs, biradicals soon became a focus of study. Biradicals are of interest because the exchange interaction between the unpaired electrons is present tliroiighoiit the biradical lifetime and, consequently, the spin physics and chemical reactivity of biradicals are markedly different from radical pairs. Work by Morozova et al [28] on polymethylene biradicals is a fiirther example of how this method can be used to separate net and multiplet effects based on time scale [28]. Figure Bl.16.11 shows how the cyclic precursor, 2,12-dihydroxy-2,12-dimethylcyclododecanone, cleaves upon 308 mn irradiation to fonn an acyl-ketyl biradical, which will be referred to as the primary biradical since it is fonned directly from the cyclic precursor. The acyl-ketyl primary biradical decarbonylates rapidly k Q > 5 x... 

As for CIDNP, the polarization pattern is multiplet (E/A or A/E) for each radical if Ag is smaller than the hyperfme coupling constants. In the case where Ag is large compared with the hyperfmes, net polarization (one radical A and the other E or vice versa) is observed. A set of mles similar to those for CIDNP have been developed for both multiplet and net RPM in CIDEP (equation (B1.16.8) and equation (B1.16.9)) [36]. In both expressions, p is postitive for triplet precursors and negative for singlet precursors. J is always negative for neutral RPs, but there is evidence for positive J values in radical ion reactions [37]. In equation (B 1.16.8),... 

Roth H D, Weng H and Herbertz T 1997 CIDNP study and ab initio calculations of rigid vinylcyclopropane systems evidence for delocalized ring-closed radical cations Tetrahedron 53 10 051-70... 

Closs G L and Czeropski M S 1977 Amendment of the CIDNP phase rules. Radical pairs leading to triplet states J. Am. Chem. Soc. 99 6127-8... 

Closs G L, Miller R J and Redwine O D 1985 Time-resolved CIDNP applications to radical and biradical chemistry Acc. Chem. Res. 18 196-202... 

Janssen and co-workers prepared t-butyl 1-pyrazolecarboxylate (111) via 1-pyrazolecar-bonyl chloride (75JOC915). The thermolysis of this compound in benzene solution at 140 °C led to 1-phenylpyrazole. The IV-pyrazolyl radical (112), which is proposed as an intermediate, proved elusive and neither CIDNP nor ESR signals were observed. 

One aspect of both EPR and CIDNP studies that should be kept in mind is that either is capable of detecting very small amounts of radical intermediates. This sensitivity makes both techniques quite useful, but it can also present a pitfall. The most prominent features of either EPR or CIDNP spectra may actually be due to radicals that account for only minor amounts of the total reaction process. An example of this was found in a study of the decomposition of trichloroacetyl peroxide in alkenes. 

Kasukhin et al. (1974) estimated a lifetime of 10-7 s for the phenyldiazenyl radical based on a CIDNP study. Later estimates of the decay rate constant were roughly in agreement with this 3.4 x 106 s 1 from the transient UV absorption in... 

Xu and Li (1989) investigated H — CIDNP spectra of fifteen substituted benzene-diazonium ions during reduction with NaBH4. The spectra are consistent with a mechanism in which the first step is the addition of a hydride ion to the diazonium ion. The diazene formed (Ar - N2 - H) is assumed to dimerize and disproportionate into a radical pair [Ar-N-NH2 N = N — Ar] which loses one equivalent of N2 yielding [Ar—N —NH2 Ar] and recombines to give the diarylhydrazine. A proportion of the aryl radicals escape and form the hydro-de-diazoniation product. 

Becker et al., (1984) investigated the photo-CIDNP effect in the presence of crown ethers (see Sec. 11.2). CIDNP studies on the photolysis (Jiang et al., 1990) and on the NaBH4 reduction (Song et al., 1990) of arenediazonium ions showed that free radical intermediates are involved. 

---