Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, VII [1]. Heterolytische Spaltung der Re-Re-Bindung in den Zweikern-Anionen [(OC)₄ReP(R₂ )O]₂ ^2- mit Elektrophilen - ein Weg zu Heterocyclen mit Re-σ-Bindung / Preparation and Properties of, and Reactions with, Metal-Containing Heterocycles, VII [1]. Heterolytic Cleavage of the Re-Re Bond in the Binuclear Anions [(OC)₄ReP(R₂)O]₂

Abstract

<jats:p>The preparation of the six-membered rhenacyclohexanes <jats:inline-formula><jats:alternatives><jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/Untitled-1.jpg" /></jats:alternatives></jats:inline-formula> (1a, b) [R = CH<jats:sub>3</jats:sub> (a), C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub> (b)] is accomplished by heterolytic cleavage of the Re-Re bond in the binuclear anions [(OC)<jats:sub>4</jats:sub>ReP(R<jats:sub>2</jats:sub>)O]<jats:sub>2</jats:sub><jats:sup>2-</jats:sup> with strong electrophiles like the alkanediylbis(triflate) (CH<jats:sub>3</jats:sub></jats:p><jats:p>)<jats:sub>2</jats:sub>C(CH<jats:sub>2</jats:sub>Y)<jats:sub>2</jats:sub> (Y = OSO<jats:sub>2</jats:sub>CF<jats:sub>3</jats:sub>). followed by an attack of the co-positioned carbenium-like C atom on the phosphinite oxygejn of the anion. 1 a, b insert SO<jats:sub>2</jats:sub> under ring expansion yielding the seven-memberod heterocyeles <jats:inline-formula><jats:alternatives><jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/Untitled-2.jpg" /></jats:alternatives></jats:inline-formula> (2a, b). 1b crystallizes triclinic in the space group P1̄ with Z = 2. Some characteristic IR and NMR data are discussed.</jats:p>