Multinuclear Ferrocenes. II. Syntheses of Substituted Biferrocenyls<sup>1-3</sup>

Goldberg, Stanley I.; Matteson, Rowland L.

doi:10.1021/jo01025a017

Cited by 15 publications

(9 citation statements)

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“…23 The atom-numbering system used for the BFD system was proposed by Goldberg and Matteson. 33 Instrumental Methods. For all cyclic voltammetry measurements (EG&G 2273 Potentiostat/Galvanostat), a conventional threeelectrode setup was used (1 mm platinum-disk working electrode, a platinum-wire counter electrode, and a silver wire as pseudoreference electrode).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Unsymmetrically Substituted 1,1′-Biferrocenylenes Maintain Class III Mixed-Valence Character

Breuer

Schmittel

2013

Organometallics

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UV−vis−near-IR electronic absorption spectra of unsymmetrically substituted derivatives of 1,1′-biferrocenylene (bis(fulvalene)diiron = BFD) have been systematically evaluated upon oxidation using spectroelectrochemical techniques. Upon reversible electrochemical oxidation to the BFD + monocation and BFD 2+ dication state, the characteristic intervalence chargeresonance (IVCR) transitions of a class III mixed-valence system in solution state was confirmed. The class III mixed-valence character of the parent BFD + system was not altered upon unsymmetric substitution. Peak-fit analysis and TD-DFT calculations were utilized to assign the observed IVCR transitions.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Unsymmetrically Substituted 1,1′-Biferrocenylenes Maintain Class III Mixed-Valence Character

Breuer

Schmittel

2013

Organometallics

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“…Preparation of Trityl /3-Naphthoate (1).-Trityl bromide (16.1 g., 0.05 mole) and sodium /3-naphthoate (10.9 g., 0.056 mole) in 70 ml. of benzene were boiled for 39 hr.…”

Section: Experimental12mentioning

confidence: 99%

“…near 350°.(1) (a) We gratefully acknowledge the generous support of the National Science Foundation, Grant 19733; (b) the paper was presented in part at the Southwest Regional Meeting of the American Chemical Society, Dec., 1963, Houston, Tex. (2) Dow Chemical Company Predoc toral Fellow, 1963-1964 (3) K.…”

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confidence: 99%

Pyrolytic and Photolytic Decomposition of Trityl β-Naphthoate¹

Berlin¹,

Rathore²

1964

J. Org. Chem.

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Pyrolysis of trityl /3-naphthoate was investigated over the range 250-350°in a static system. Although the decomposition was examined after long time intervals, the process was essentially complete within an interval of 1.5 hr. Both acyl-oxygen and alkyl-oxygen bond severance occurred as evidenced by the major products, /3-naphthoic acid, /3-naphthoic anhydride, triphenylmethane (tritane), and two polymers, one a hydrocarbon and the other a polyester. Minor products observed were carbon dioxide, carbon monoxide, water, naphthalene, benzophenone, 9-phenylfluorene, and an unknown gas. Oxidation of the melt resulted in a marked increase in benzophenone. Although photolysis of the ester in an oxygen atmosphere resulted in limited decomposition, benzophenone was identified in the photolysate. A radical mechanism is postulated to explain the data.As part of a program to elucidate the chemistry of aroyloxy radicals generated under pyrolytic conditions, trityl /3-naphthoate was considered important since little has been published on /3-naphthoxyloxy radicals.In view of the preference of trityl radical to abstract hydrogen rapidly at elevated temperatures,3 naphthyue was envisioned as a possible intermediate via removal of the -hydrogen and loss of carbon dioxide.4•5 Moreover, trityl /3-naphthalene is a conceivable product since the homolog, trityl benzoate, is recorded to decompose at 235°with tetraphenylmethane formed in moderate yields.6•7 The simplicity of decomposition as depicted in Scheme I was not observed, however.Trityl /3-naphthoate (1) was prepared by an extension of the method described previously.8 Recently we reported the pyrolysis of several trityl alkyl carboxylates from which acyl-oxygen and alkyl-oxygen bond cleavages were observed.3 Thermal decomposition of 1 was conducted in a static system over the range 250-350°under nitrogen. It was discovered that the ester decomposed completely within 1.5 hr. near 350°.(1) (a) We gratefully acknowledge the generous support of the National Science Foundation, Grant 19733; (b) the paper was presented in part at the Southwest Regional Meeting of the American Chemical Society, Dec., 1963, Houston, Tex. (2) Dow Chemical Company Predoc toral Fellow, 1963-1964 (3) K.

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“…1 Hz; the signals of the methoxymethine protons of the diastereomers derived from 5 were separated by ca. 2 Hz. The chemical shift nonequivalence of the diastereo topic methoxymethine protons derived from 5 could therefore be used as the basis for estimating the optical purity by nmr.…”

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confidence: 99%

“…This result is contrary to expectations since, even taking into account that the values cited for 1 and 2 refer to different solvents (hydrocarbon and ethanol, respectively), 1 and 2 do have similar chromophoric geometries and the rotational strengths should clearly manifest parallel behavior in ORD and CD. 2 In terms of the semiquantitative expression relating molecular amplitude and circular dichroism of ketones,8 [0]max values of +6.4 and -6.9 X 104 might have been predicted from the a values of 1 and 2, respectively, or, conversely, a values of +390 and -720 might have been predicted from the reported [0]max values of 1 and 2, respectively. Whereas calculated (1) (a) This work was supported by the Air Force Office of Scientific Research under Grant No.…”

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confidence: 99%