Reaction of carbonyl groups with perchloric acid. Gem-diperchlorates

Reaction of carbonyl groups with perchloric acid. Gem-diperchlorates. Kurt Baum. J. Am. Chem. Soc. , 1970, 92 (9), pp 2927–2928. DOI: 10.1021/ja0071...
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L, may be neutral molecules or anions, or may be absent), provide circumstances well suited to the study of the strength and nature of metal-to-metal (M-M) interactions as a function of electron configuration, formal charge, and position in the periodic table. The metal atoms are relatively free to move over fairly wide limits along the fourfold axis in accord with the magnitude and sign of the interaction between them. Thus, in a variety of copper(I1) compl5xes the Cu-Cu distances2r3 are in the range 2.62-2.71 A, indicative of only slight interaction. Magnetic studies3 confirm that only weak antiferromagnetic spin couplings occur. In M O , ( O ~ C C Hand ~ ) ~several ~ Rez(OzCR)4Xzspecies,jI6 on th? other hand, exgemely short distances (Mo-Mo, 2.11 A ; Re-Re, 2.24 A) imply very strong M-M interactions which can be formulated as quadruple bonds. 1*7 Chromous acetate, Cr2(02CCH3)1(H20)2, has always been regarded as exhibiting very weak M-M interaction. The structure was reporteds t o be similar , O ) ~ a Cr-Cr distance to that ,Of C U ~ ( O ~ C C H , ) ~ ( H with of 2.64 A. Even though the compound is diamagneti~,~ such a distance has been regardedl~g~lo as too long to allow for substantial M-M bonding. Thus Figgis and Marting concluded that “since the internuclear Cr-Cr distance is identical to that observed in copper acetate, the bonds (i.e., u, a and 6 components of a quadruple interaction) are unlikely to be strong. This conclusion is supported by evaluation of the oyerlap integrals.” Of course, at the distance of 2.64 A the overlap integrals had to be very small. Similarly, Cotton’ wrote: “Is there any more involved (in Cr2(02CCH,)1(H20)2)than just interionic coupling of spins? Is there actually a Cr-Cr b p d ? The structural parameters ( i x . , Cr-Cr = 2.64 A) indicate clearly that there is no bond.” More recently, however, various considerations led us to question the reasonableness of the seemingIy proved weakness of the Cr-Cr interaction. A critical examination of the report on the structureg raised grave doubts as to its reliability; the reported distance appeared to be only a rough estimate, arbitrarily L. Manojlovic-Muir, Chem. Commun., 1057 (1967). D. M. L. Goodgame, et al., ibid.,629 (1969). D. Lawton and R. Mas0n.J. Amer. Chem. Soc., 87,921 (1965). M. J. Bennett, W. I