Coordination Behavior of [Cp′′₂Zr(η^1:1‐P₄)] towards Different Lewis Acids

Abstract

A detailed method for the preparation of [Cp'' Zr(η -P )] (1) is presented. The coordination behavior of 1 towards Lewis acidic transition metal complexes of tungsten, manganese, and iron, respectively, and main group compounds (AlMe , AlEt ) was investigated in detail by computational and experimental studies. In doing so, a series of unprecedented complexes with different coordination modes and multiple coordination numbers of the tetraphosphabicyclo[1.1.0]butane framework were synthesized. All products, as well as the starting materials, were comprehensively characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single crystal X-ray structural analysis.

Coordination Behavior of [Cp″2Zr(µ1:1-As4)] towards Lewis Acids

“…Recently, we investigated the coordination behavior of [Cp″ 2 Zr(η 1:1 -P 4 )] towards Lewis-acidic metal fragments [ 27 ]. The results show that a coordination to Lewis acids via both the wing tip and bridgehead phosphorus atoms is possible, with the coordination via the wing tip P atoms being favored electronically but disfavored sterically.…”

“…Further investigations illustrate the high potential of 1 as an arsenic transfer reagent [ 24 , 25 , 26 ]. Additionally, the phosphorus congener of 1 , i.e., [Cp″ 2 Zr(η 1:1 -P 4 )], shows diverse reactivity patterns towards Lewis acids [ 27 ]. These results led us to investigate the reaction behavior of 1 towards the same Lewis acids to possibly functionalize the As 4 core in 1 .…”

Dual Functionalization of White Phosphorus: Formation, Characterization, and Reactivity of Rare‐Earth‐Metal Cyclo‐P3 Complexes

“…To evaluate the coordination behaviors of these novel complexes, Group 6 metal carbonyl compounds were applied . Treatment of 2 a , b with [W(CO) 5 (THF)] resulted in the formation of 4 a , b , respectively (Scheme ).…”

Dual Functionalization of White Phosphorus: Formation, Characterization, and Reactivity of Rare‐Earth‐Metal Cyclo‐P3 Complexes

“…[7d, 16] This nucleophilic mechanism shows the first P 4 degradation pathway involving rare-earth metal fragments,w hile the rare-earth metalmediated reductive P 4 activation pathway usually generates aggregation products. [20] Tr eatment of 2a,b with [W(CO) 5 (THF)] resulted in the formation of 4a,b,respectively (Scheme 4). [1,19] To evaluate the coordination behaviors of these novel complexes,G roup 6m etal carbonyl compounds were applied.…”

“…[1,19] To evaluate the coordination behaviors of these novel complexes,G roup 6m etal carbonyl compounds were applied. [20] Tr eatment of 2a,b with [W(CO) 5 (THF)] resulted in the formation of 4a,b,respectively (Scheme 4). According to the solid-state structures (Figure 4f or 4a,s ee the Supporting Information for the X-ray structure of 4b), only P1 coordinates to [W(CO) 5 ]o wning to its anionic property.…”