2,4-dimethylene-1,3-cyclobutanediyl and 2,4-dimethylenebicyclobutane. Synthesis, spectroscopy, and reactivity of a triplet biradical and its covalent isomer

The preparation and direct observation of triplet 2,4-dimethylene-1,3- cyclobutanediyl (1), the non-Kekule isomer of benzene, is described. The biradical was generated by photolysis of 5,6-dimethylene-2,3- diazabicyclo[2.1.1]hex-2-ene (2) (which was synthesized in several steps from benzvalene) under cryogenic, matrix-isolation conditions. Biradical 1 was characterized by EPR spectroscopy (‌‌‌‌‌│D/hc│ =0.0204 cm^(-1), │E/hc│ =0.0028 cm^(-1)) and found to have a triplet ground state. The Δm_s= 2 transition displays hyperfine splitting attributed to a 7.3-G coupling to the ring methine and a 5.9-G coupling to the exocyclic methylene protons. Several experiments, including application of the magnetophotoselection (mps) technique in the generation of biradical 1, have allowed a determination of the zero-field triplet sublevels as x = -0.0040, y = +0.0136, and z = -0.0096 cm^(-1), where x and y are respectively the long and short in-plane axes and z the out-of-plane axis of 1.

Triplet 1 is yellow-orange and displays highly structured absorption (λ_(max)= 506 nm) and fluorescence (λ_(max) = 510 nm) spectra, with vibronic spacings of 1520 and 620 cm^(-1) for absorption and 1570 and 620 cm^(-1) for emission. The spectra were unequivocally assigned to triplet 1 by the use of a novel technique that takes advantage of the biradical's photolability. The absorption є = 7200 M^(-1) cm^(-1) and f = 0.022, establishing that the transition is spin-allowed. Further use of the mps technique has demonstrated that the transition is x-polarized, and the excited state 1s therefore of B_(1g) symmetry, in accord with theoretical predictions.

Thermolysis or direct photolysis of diazene 2 in fluid solution produces 2,4- dimethylenebicyclo[l.l.0]butane (3), whose ^(l)H NMR spectrum (-80°C, CD_(2)Cl_(2)) consists of singlets at δ 4.22 and 3.18 in a 2:1 ratio. Compound 3 is thermally unstable and dimerizes with second-order kinetics between -80 and -25°C (∆H^(‡) = 6.8 kcal mol^(-1), (∆s^(‡) = -28 eu) by a mechanism involving direct combination of two molecules of 3 in the rate-determining step. This singlet-manifold reaction ultimately produces a mixture of two dimers, 3,8,9- trimethylenetricyclo[5.1.1.0^(2,5)]non-4-ene (75) and trans-3,10-dimethylenetricyclo[6.2.0.0^(2,5)]deca-4,8-diene (76t), with the former predominating. In contrast, triplet-sensitized photolysis of 2, which leads to triplet 1, provides, in addition to 75 and 76t, a substantial amount of trans-5,10- dimethylenetricyclo[6.2.0.0^(3,6)]deca-3,8-diene (77t) and small amounts of two unidentified dimers.

In addition, triplet biradical 1 ring-closes to 3 in rigid media both thermally (77-140 K) and photochemically. In solution 3 forms triplet 1 upon energy transfer from sensitizers having relatively low triplet energies. The implications of the thermal chemistry for the energy surfaces of the system are discussed.

The streaming of 1.3-2.3 MeV cosmic-ray protons during periods between prompt solar particle events

The anisotropy of 1.3 - 2.3 MeV protons in interplanetary space has been measured using the Caltech Electron/Isotope Spectrometer aboard IMP-7 for 317 6-hour periods from 72/273 to 74/2. Periods dominated by prompt solar particle events are not included. The convective and diffusive anisotropies are determined from the observed anisotropy using concurrent solar wind speed measurements and observed energy spectra. The diffusive flow of particles is found to be typically toward the sun, indicating a positive radial gradient in the particle density. This anisotropy is inconsistent with previously proposed sources of low-energy proton increases seen at 1 AU which involve continual solar acceleration.

The typical properties of this new component of low-energy cosmic rays have been determine d for this period which is near solar minimum. The particles have a median intensity of 0.06 protons/ cm^(2)-sec-sr-MeV and a mean spectral index of -3.15.The amplitude of the diffusive anisotropy is approximately proportional to the solar wind speed. The rate at which particles are diffusing toward the sun is larger than the rate at which the solar wind is convecting the particles away from the sun. The 20 to 1 proton to alpha ratio typical of this new component has been reported by Mewaldt, et al. (1975b).

A propagation model with κ_(rr) assumed independent of radius and energy is used to show that the anisotropy could be due to increases similar to those found by McDonald, et al. (1975) at ~3 AU. The interplanetary Fermi-acceleration model proposed by Fisk (1976) to explain the increases seen near 3 AU is not consistent with the ~12 per cent diffusive anisotropy found.

The dependence of the diffusive anisotropy on various parameters is shown. A strong dependence of the direction of the diffusive anisotropy on the concurrently measured magnetic field direction is found, indicating a κ_⊥ less than κ_∥ to be typical for this large data set.