Phosphines protonation shifts

BioH14 is a mdo-polyborane, therefore, it is expected that it forms adducts with Lewis bases. This is indeed the case but with concomitant loss of hydrogen as shown in Eq. (51). These adducts of the type BioHi2-2L (L = amines, pyridine, phosphines, nitriles, dialkylsulfides inter alia) proved to be versatile reagents. For instance, when triethylamine is used to replace acetonitrile from the adduct not only does the expected replacement occur but in preference also a proton shift (most likely prior to the base displacement reaction) with cluster closure to the decahydro-doso-decaborate(2—) (Eq. 52) ... 

This rearranges by proton shift to the 2-hydro-phosphinic acid 85b, two molecules of which associate by hydrogen bridging to the dimer. The long-wave maximum at 275 nm (e = 4075), (Amax2 = 237 nm, e = 2925) confirms the phospha-cyclohexadiene (2,4) system. 

The interactions of LSR with various organophosphorus substrates have been reported (460-463). Yb(fod)3 and Pr(fod), are considered to be the best LSR for organophosphorus compounds. Proton shifts are, as usual, dominated by pseudocontact interactions. shifts are predominantly pseudocontact in nature but have sizeable contact contributions for phosphine and phosphoryl compounds. In contrast P shifts have large contact components where direct phos-phoryl-oxygen or phosphorus-lanthanide interactions occur. Large pseudocontact P shifts for triethyl phosphite indicate little or no direct phosphorus-lanthanide interaction. 

An exception to the straightforward correspondence between C shifts in zeolites (or other catalysts) and solution values occurs when the structure of the compound is significantly perturbed on the catalyst. The most common example is protonation equilibria on acidic catalysts. Indeed, there have been a number of reports of the use of protonation shifts of amines 151,521, phosphines (151, and phosphine oxides (531 as probes of catalyst acidity. Similar effects are (x ca-sionally encountered in in situ experiments when a basic molecule is formed as an intermediate or product. An interesting case is the conversion of acetone to hydrocarbons on zeolites, which may involve the intermediacy of diacetone alcohol, mesityl oxide, phorone, and isophorone—all ketones. The chemical shifts of the carbonyl carbons of all these species in acidic zeolites were found to be up to 10 ppm downfield of the corresponding values in reference compilations. Furthermore, although the chemical shifts of the olefinic carbons a to the carbonyl were in reasonable agreement with values for CDCI solutions, the resonances of the olefinic carbons p to the carbonyl were very broad and shifted 20-30 ppm downfield 54. ... 

A more serious complication for the betaine mechanism arose when it was found that oxaphosphetanes are more stable than betaines. The earliest evidence was encountered by Ramirez et al. (17), who found that certain phosphines react with two equivalents of hexafluoroacetone to give 1,3,2-dioxaphospholane derivatives 23 (Scheme 6). These compounds rearrange into unusually stable oxaphosphetanes 26 via fragmentation to 24, followed by a proton shift to generate an intermediate ylide 25 (17). Shortly thereafter, Vedejs and Snoble (18) used P nuclear magnetic resonance (NMR) methods to show that more typical Wittig reactions of nonstabilized ylides PhjP CHR also produce oxaphosphetanes and that these intermediates can be easily observed at temperatures below 0°. Since betaines did not accumulate in any of the experiments, their conversion to oxaphosphetanes could not be rate... 

The mechanism for both methods is similar and has been proposed to begin with the conjugate addition of the phosphine to the Michael electrophile (i.e., allenoate or2-aUcynoate). In Scheme 33 the mechanism describing the transformation of 2-aIkynoate is presented. After Michael addition, protons shift of the Michael adduct leads eventually to phosphonium ylide 57 that would react in a Wittig reaction with an aldehyde and displace the previous equilibria. Note that, despite the elevated temperature of the reaction with 2-aIkynoate, no isomerization of the double bond allowing the conjugation of the ester with the double bonds was observed. 

A method for determining the basicities of phosphoryl compounds has been decribed which is based on 31P n.m.r. chemical shift measurement and a two phase system consisting of an organic solvent and 12H sulphuric acid.245 The gas-phase protonation of aliphatic phosphine oxides have been determined by cyclotron resonance. There was a good correlation of pK4 with Kabachnik constants and HO... 

The basicity of halogenophosphines has attracted some attention this year. A careful study of the protonation of several halogenophosphines (6) has led to the characterization by 31P n.m.r. of phosphonium species, such as (7).12 These salts show 31P shifts to relatively high fields, and large Vph values e.g., (7) has 1190 Hz.12 Attempts have been made to correlate phosphine basicity with Vpb values in borane complexes,13 and, in turn, to correlate Vpb with electrostatic interactions in the phosphorus-boron bond.13 From such correlations, the authors deduce that this bond is dominated by electrostatic contributions, and not by other factors, such as -bonding. 

Fields et al. 33) examined the closely related bis (trifluoromethyl) phosphine (Table 14) and found a similar increase in Vp.H with increasing polarity of the solvent. They noted a correlation between /P H and the proton chemical shift (confidence limit of the correlation coefficient was 99.9 %). Again hydrogen bonding was suggested as the principle causative factor since correlations with dielectric constant or refractive index were not found. The two-bond 2/P F was noted to decrease while the three-bond 3/H F coupling constant was solvent invariant (vide infra). 

Also fluorosulphonic acid protonates phosphine as well as organophos-phines. The phosphonium ions formed are soluble in fluorosulphonic acid. The chemical shifts, 631P and 61, of phosphine, the phosphonium ion and a series of organophosphines and the respective cations obtained by protonation are shown in Table 4. 

Hydroxy(alkoxy)phosphonium Ions. Olah and McFarland560 studied the protonation in HS03F or HS03F-SbF5 solution of varied phosphorus oxyacids and derivatives. Treatment of tetravalent phosphoms compounds (phosphorus, phosphonic, and phosphinic acid and their trialkyl and triaryl derivatives) results in (9-protonation and the formation of hydroxyphosphonium ions. Trivalent phosphites, in turn, are protonated at the phosphorus atom. The 31P shifts observed for the latter ions are significantly deshielded, which was attributed to significant oxonium ion character. 

It seems likely that the magnitude of p represents the "extent of electron demand at phosphorus , in the T. S. or in other words is a measure of "electron transfer" in the T.S., a term (=z) which appears in the semi-empirical equations describing the nucleophilic reactivity of tricoordinated phosphorus. This concept is reinforced by (i) the observation (from the data of Bokonov. and Goetz ) that p-values based on the pKg values of protonated phosphines increase with increasing pKa, i.e. increase with a shift of the equilibrium (eqn. 4) to the left and... 

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