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Decomposition of 2-diazo-l,3-indandione (3) by rhodium(II) acetate (1) in cyclohexane and in benzene results in overall carbon-hydrogen insertion to give 2-substituted 1,3-indandiones. Anisóle, 1, and 3 yield 2-(4-methoxyphenyl)-l,3-indandione (74%); benzenes substituted by single methyl or halogen groups yield the corresponding orthoand para-substitution products. Spirocyclopropanes are obtained by rhodium(II)-catalyzed additions of 3 to olefins; electron-deficient olefins do not give adducts. Substituted 4/f-indeno[ 1,2-6]furan-4-ones and 2,3-disubstituted spiro[cyclopropene-l,2'-[2H]indene]-l',3'-diones are formed from rhodium(II)-catalyzed reactions of 3 with acetylenes. Reactions of 1 and 3 with cyclohexane, olefins, acetylenes, and arenes involve selective electrophilic carbenic or y lidie processes. 2-Diazo-l-indanone (4) is converted by 1 to 2,2'-bis[indan-l-one] (48). Thiophenol reacts with 4 and 1 to yield 2-(phenylthio) -1 -indanone (49). Cyclopropanations of cyclohexene and styrene by 4 as catalyzed by 1 result in spiro[bicyclo[4.1.0]heptane-7,2'-[27f]indan]-l-one (50) and 2 -phenylspiro[cyclopropane-l,2'-[2H]inden]-1'(3'77)-one (51), respectively.

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Removal of the solvent left 8 mg (90%) of a mixture of anti-(CH3,C1)B (27%) and (CH3,Cl)(CH3,Cl)lactone (73%) as determined by NMR.Conversion of (CH3,CH3)(CH3,CH3)lactone to anti-(CH3,CH3)B. The lactone (28 mg, 0.15 mmol), initially a suspension, was stirred in sodium hydroxide (15 mL, 0.1 , 1.5 mmol) for 2 h, the light yellow solution was acidified (ca. pH 2.5), the solution was stirred for a few hours and then extracted with CHC13, the extract was dried (MgS04), and the solvent was removed to yield 26 mg (93%) of anit-(CH3,CH3)B (90%) and lactone (10%) as shown by NMR.A similar experiment with (CH3CH2,CH3)(CH3CH2,CH3) lactone yielded onti'-(CH3CH2,CH3)B (79%) and lactone (21%).Rate Measurements. Low Rates. Bimane in CH3CN (0.1 mL) was added to temperature-equilibrated buffer (3 mL) contained in a quartz cell. The absorption spectrum was measured with a Cary Model 17 spectrophotometer. For several syn-bimanes, fluorescence spectra were recorded with a Hitachi-Perkin-Elmer MPF 4.High Rates. The bimane solution was added to the buffer being stirred by a small Teflon-coated bar moved by a small motor mounted below the cell holder with the chart paper running and the wavelength fixed at the absorption maximum. Smooth curves were usually observed after 1-2 s (mixing time). Sodium phosphate (pH 7-8) and sodium carbonate (pH 9-10) buffers were used. The pH values were measured at 25 °C and corrected to 50 °C with temperature factors recorded in the literature.31