Addition Reactions of Maleic Anhydride to a Disilene and a Tetrasilabuta-1,3-diene:  Formation of Bi- and Tetracyclic Compounds^1,2

Chemical manipulation of multifunctional hydrocarbons on silicon surfaces

“…In the views of chemists, Si=Si should obviously make a much better model of a silicon dimer on a Si(100)-2×1 surface than C=C. Although the comparison should definitely be treated with caution and although the number of chemical reactions studied with disilenes fades in comparison with the number of reactions investigated with alkenes, the predictions for -NO 2 , -NO, -N 3 , O 2 , and several other cycloaddition reactions with Si(100)-2×1 were accurate, based on the reactions with disilenes reported by Gillette et al in the late 1980s and in early 1990 s [37][38][39] and reactions of Si(100)-2×1 with alkenes and dienes were very similar to the chemistry reported by several groups [40][41][42][43][44] and reviewed by Weidenbruch [45][46][47][48]. Especially noteworthy is the fact that the processes following the initial attachment chemistry can also be compared quite reliably.…”

“…Thus, as opposed to a [2 + 2] scheme postulated for simple monounsaturated compounds on this silicon surface, maleic anhydride reacts by a more complex [1 + 2 + 1] addition, forming product II, which was shown to be the energetic minimum at low coverage [206]. It is interesting to remark that the attempt to predict the outcome of interaction of maleic anhydride with the Si(100)-2×1 surface based on the knowledge of homogeneous chemistry of this compound with disilenes would fail miserably as it has been shown that disilenes react with the C=O group to form a somewhat complex adduct and that this transformation is followed by a 1,2-hydrogen shift [44].…”

From a Cyclotrisilane to a Cyclotriplumbane: Low Coordination and Multiple Bonding in Group 14 Chemistry

“…An exception is the reaction of 61 with maleic anhydride, which furnished the tetracyclic compound 62 in high yield. It can be assumed that the reaction sequence is initiated by a [2 + 2] cycloaddition of one of the SiSi double bonds to the highly reactive CO group, followed by a second cycloaddition of the remaining SiSi bond across the CC double bond to complete the formation of 62 (Scheme ) 14 …”

Mechanism of the Addition of Nonenolizable Aldehydes and Ketones to (Di)metallenes (R2XYR2, X = Si, Ge Y = C, Si, Ge): A Density Functional and Multiconfigurational Perturbation Theory Study

“…Although there are some notable exceptions, in general, nonenolizable ketones and aldehydes add to (di)metallenes to yield (di)metalloxetanes as shown in Scheme . − ,− ,− Metalloxetanes are of chemical interest as reactive intermediates because they undergo metathesis reactions. Such reactions are of synthetic value because they may provide an alternative of means of forming CC and YC bonds, where Y is Si or Ge, as well as metallanones containing XO bonds, where X is Si or Ge, which are also of significant chemical interest.…”