Heterodiatomic Multiple Bonding in Group 13: A Complex with a Boron–Aluminum π Bond Reduces CO₂

Abstract

Heterodiatomic multiple bonds have never been observed within Group 13. Herein, we disclose am ethod that generates [(CAAC)PhB=AlCp 3t ]( 1), ac omplex featuring p bonding between boron and aluminum through the association of singlet fragments.W epresent the properties of this multiple bond as well as the reactivity of the complex with carbon dioxide,w hichy ields ab oron CO complex via an unusual metathesis reaction.

Aluminium‐Mediated Carbon Dioxide Reduction by an Isolated Monoalumoxane Anion

“…[15] More recently,i th as been shown that am ultiply bonded Al-B compound effects CO 2 reduction to give boron-carbonyl species VIII,proceeding with loss of the Al fragment. [16] Theu tilization of aluminum in this area is particularly attractive due to its low cost and high terrestrial abundance. Recent advances in group 13 chemistry have led to the development of new nucleophilic sources of aluminum [17] and indium.…”

Crystalline Boragermenes

“…In particular, the chemistry of heteroatomic multiple bonds between boron and other p‐block elements has attracted significant attention, reflecting their unique electronic and structural properties, reactivities, and their associated potential use as building blocks. Over the past few decades, a myriad of compounds involving a double bond between boron and other elements, such as Al, a pnictogen (N, P, and As), or a chalcogen (O, S, Se, and Te), in addition to transition metals, have been developed and extensively studied . In terms of derivatives with Group 14 elements, Nöth et al.…”

Stabilisierung planarer Cyclopenten‐4‐yl‐Kationen durch Hyperkonjugation und π‐Delokalisierung

“…In dieser Arbeit stellen wir unsere Studien zur Aufklärung der elektronischen Struktur von Cyclopenten‐4‐yl‐Kationen vor. Im Rahmen unserer Forschungsarbeiten auf dem Gebiet Cp‐substitutierter Aluminiumspezies‐ ist uns nun die Generierung zweier stabiler Derivate des planaren Cyclopenten‐4‐yl‐Kations 1 C gelungen. Deren hohe Stabilität und regioselektive Bildung geht hierbei vor allem auf starke Hyperkonjugationswechselwirkungen zwischen den C‐Al‐ und C‐Si‐σ‐Bindungen und den unbesetzten p‐Orbitalen der kationischen sp 2 ‐Kohlenstoffzentren zurück.…”