NMR spectroscopy and crystal structure of [Me2GaP(H)SitBu3]2 and theoretical investigations of the model compounds

Synthesis, Structures and Thermal Decomposition of Monomeric Aluminium, Gallium and Indium Silylphosphanides

“…As shown in our own work with [Et 2 GaP(H)Si(Me 2 )(CMe 2 i Pr)] 2 , smaller substituents at both gallium and phosphorus provide the same structure 7a. Similar results were obtained by Westerhausen et al with the compound [Me 2 GaP(H)Si t Bu 3 ] 2 when using a combination of huge substituents at the silyl groups and small ones on gallium 9. Analogously to both mentioned structures, compound 1 also shows cis and trans isomers in solution in a ratio of 1:1.…”

“…A few years ago, we succeeded in preparing two cyclic compounds, [Et 2 InP(H)Si i Pr 3 ] 2 ( I ) and [Et 2 GaP(H)SiMe 2 CMe 2 i Pr] 2 ( II ), which contain hydrogen atoms at the phosphorus 7. Similar structures that involve aluminium have been obtained by Cowley et al and also by the Schulz's group (Scheme ) 8,9…”

A Sterically Encumbered 13/15 Cycle and its Cleavage with N‐heterocyclic Carbenes and other Lewis Bases

“…Formally described as diphosphidogallate, this anion shows an average P–Ga bond length of 246.3 pm. This fits to Ga–P bond lengths in four‐membered cycles of the type [ R 2 GaP(H) R ′] 2 ,, even though the phosphorus atoms are only threefold bounded in compound 4 . With 203.9 pm, the average Ga–C bond length in 4 lies within the range of similar gallanate anions ([Ga t Bu 4 ] – : 202.5 pm, [GaBn 4 ] – : 204.1 pm, or [Ga(CH 2 SiMe 3 ) 4 ] – : 204.5 pm) and together with the Ga‐surrounding angles of 94.9–119.3° it supports the description as a distorted tetrahedral [Ga t Bu 2 (P(H)SiR 3 ) 2 ] – anion.…”

Reactions of tBu2AlH and RE(SiMe3)2 (R = H, SiMe3) – Synthesis and X‐ray Crystal Structures of [tBu2AlP(H)SiMe3]2 and [tBu2AlE(SiMe3)2]2 (E = Sb, Bi)

“…To the best of our knowledge, 3 represents the first structurally characterized dimeric phosphanylalane containing primary phosphido ([RPH] – ) bridges 26. Comparable phosphanylgallanes [R 2 GaPHR′] 2 were shown to form either planar ([Cl 2 GaP(H)Si( t Bu) 3 ] 2 ,27 [ t Bu 2 GaP(H) t Bu] 2 ,28 [ t Bu 2 GaP(H)Cp] 2 29) or butterfly‐type ring structures ([Me 2 GaP(H)Si( t Bu) 3 ] 2 27). The formation of a four‐membered ring is caused by the steric demand of the t Bu substituents, as can be seen when comparing 3 with sterically less hindered phosphanylalanes [(Me 2 Al) 3 (P(H)SiMe 3 ) 2 P(SiMe 3 ) 2 ]13 and [Me 2 AlP(H)Si( i Pr) 3 ] 2 ,30 which form six‐membered rings in the solid state.…”