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The reaction between the heteroleptic metal carbonyl complex [W(CO)4(tmeda)] ((tmeda)=N,N,N′,N′‐Tetramethylethane‐1,2‐diamine) with [Si9]4− silicon Zintl clusters in presence of [2.2.2]crypt ([2.2.2]crypt=4,7,13,16,21,24‐Hexaoxa‐1,10‐diazabicyclo[8.8.8]‐hexacosane) in liquid ammonia yielded the compound [(K,Rb)@([2.2.2]crypt)]2(K,Rb)4[Si9W(CO)4] ⋅ 13.4 NH3. The compound was analyzed by single crystal X‐ray diffraction and crystallizes in the space group P1‾ ${P\bar{1}}$ (a=11.48390(10) Å, b=19.7383(2) Å, c=19.8983(2) Å, α=112.5760(10)°, β=97.4210(10)°, γ=95.3760(10)°, V=4079.01(7) Å3). The compound represents the first group 6 carbonylate‐functionalized silicon Zintl cluster. The central moiety is composed of a tricapped trigonal prismatic nine‐atom silicon species which coordinates with the lone pair of one capping atom to the tungsten tetracarbonylate, forming a pseudo trigonal bipyramidal carbonylate cluster anion [Si9W(CO)4]6−. The chemical bonding in the new cluster entity is analyzed using theoretical calculations and subsequent analysis using QTAIM and NBO. [ABSTRACT FROM AUTHOR]

The hydrostannylation of white phosphorus (P 4 ) allows this crucial industrial precursor to be easily transformed into useful P 1 products via direct, 'one pot' (or even catalytic) procedures. However, a thorough mechanistic understanding of this transformation has remained elusive, hindering attempts to use this rare example of successful, direct P 4 functionalization as a model for further reaction development. Here, we provide a deep and generalizable mechanistic picture for P 4 hydrostannylation by combining DFT calculations with in situ 31 P NMR reaction monitoring and kinetic trapping of previously unobservable reaction intermediates using bulky tin hydrides. The results offer important insights into both how this reaction proceeds and why it is successful and provide implicit guidelines for future research in the field of P 4 activation., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)