Activation of Di‐tert‐butyldiphosphatetrahedrane: Access to (tBuCP)_n (n=2, 4) Ligand Frameworks by P−C Bond Cleavage

Abstract

The first mixed phosphatetrahedranes were reported only recently and their reactivity is virtually unexplored. Herein, we present a reactivity study on di‐tert‐butyldiphosphatetrahedrane (1), which is the dimer of tert‐butylphosphaalkyne. The (tBuCP)2 tetrahedron is activated selectively by N‐heterocyclic carbene (NHC) nickel(I) and nickel(0) complexes, resulting in novel complexes featuring diverse (tBuCP)n‐frameworks (n=2, 4). Release of the (tBuCP)4 framework from one of the complexes was achieved by addition of CO gas. Furthermore, 1 can be used as a source for P2 units by elimination of di‐tert‐butylacetylene in the coordination sphere of nickel.

A Homoleptic Diphosphatetrahedrane Nickel(0) Complex

“…Thus, reactions with anionic metalates of Fe and Co afforded η 4 ‐coordinated diphosphacyclobutadiene complexes [10a] . Similar diphosphacyclobutenediide ligands were formed when reacting ( t BuCP) 2 with Ni(0) and Ni(I) NHC complexes, showing planar t Bu 2 C 2 P 2 2− units which are σ‐coordinated to Ni atoms [10c] . Only two complexes with intact phosphatetrahedrane moieties have been structurally characterized so far.…”

Zugang zu (tBuCP)n‐Gerüsten (n=2, 4) durch P‐C‐Bindungsspaltung von Di‐tert‐butyldiphosphatetrahedran

“…Molekülstrukturen von 2 (links), 3 a (Mitte) und 3 b (rechts) im Festkçrper. [19] Die Schwingungsellipsoide entsprechen einer Aufenthaltswahrscheinlichkeit von 50 %. Bei 2 ist nur ein Molekül der asymmetrischen Einheit gezeigt.…”

“…Dimerisierung von 1 in der Koordinationssphäre von [(IMes) 2 Ni] (oben) und Molekülstruktur von 4 im Festkçrper (unten). [19] Die Schwingungsellipsoide entsprechen einer Aufenthaltswahrscheinlichkeit von 50 %. Wasserstoffatome und Lçsungsmittelmoleküle und eine fehlgeordnete Komponente (P2B und P3B) sind nicht gezeigt.…”

Access to 1,2,3-triphospholide ligands by reduction of di-tert-butyldiphosphatetrahedrane

“…6,7 This has inspired the study of the reaction chemistry of A-C, which has revealed some similarities, but also differences with respect to the chemistry of white phosphorus in particular. [3][4][5][8][9][10][11][12][13][14] Isomerisations of the phosphatetrahedrane scaffold have been observed in reactions with main group nucleophiles. Thus, N-heterocyclic carbenes (NHCs) effect P-C or P-P bond cleavage in A, giving bis( phosphaalkenes) or phosphirenes depending on the NHC (Fig.…”