X-Ray structure of the 1,2-dioxetan dispiro(adamantane-2,3′-[1,2]dioxetan-4′,2′-adamantane)

Abstract

X-Ray data for dispiro(adamantane-2,3'-[1,2]-unusual stability of the dispiro-1,2-dioxetan (I) .4 X-Ray data for this class of compounds will be useful in any careful evaluation of the steric requirements of 1,2-dioxetans in bioluminescent ~y s t e r n s . ~ Our own need for these THE chemiluminescent decomposition of 1,2-dioxetans is data is evident from our recent studies.2 We therefore the subject of continuing study.l v 2 Structural parameters report the X-ray crystal structure of dispiro (adamantanecan be helpful in substantiating the proposed reason3 for the 2,3'-[1,2]dioxetan-4', 2''-adamantane) (I). dioxetan-4',2"-adamantane) are presented and support suggestions regarding the reasons for its unusual stability.

Chemiluminescence of dioxetanone investigated by self-consistent-field theory

“…The oxygen-oxygen bond length is somewhat longer than that determined by X-ray crystallography for adamantylideneadamantane-l,2-dioxetane (Q) by Wynberg and coworkers. 12 However, the most surprising feature of the predicted structure of dioxetanone is that the atoms of the four membered ring are found to be essentially coplanar. This finding is in contrast to the structure of dioxetane , in which one oxygen atom of the peroxide is lifted ca.…”

Chemiluminescence of Organic Compounds

“…1,2-Dioxetanes suchi as 3 generate excited sf-,ite ;'.rhonvl prodiiits with high efficiency, and it has been noted that their geometry approaches that expected for the excited state of the carbonyl products (Numan et al, 1977 is the excited state at the relaxed geometry is not acessible, then the crossing between the ground and excited state must occur at a non-relaxed geometry, one of higher energy. Thus a geometry factor, AE' must be added to the energy requirement:…”

Oxygenation of Phenanthriporphyrin and Copper(III) Phenanthriporphyrin: An Efficient Route to Phenanthribilinones

“…Oxygen–oxygen bond lengths in optimized 1-Cu c -2 , 1-Cu t -2 , 2-Cu c -2 , and 2-Cu t -2 (1.49 Å) are comparable with those observed in the X-ray structures of 1,2-dioxetanes. − 1,2-Dioxetane rings ( 1-Cu c -2 , 1-Cu t -2 , 2-Cu c -2 , and 2-Cu t -2 ) exhibit a typical, nonplanar (puckered) conformation. − …”