Herein, we present the synthesis and characterisation of new group 15 element compounds with low valent phosphorus atoms as substituents. This new series of compounds includes the heavier group 15 elements and represents the rare group of compounds with a direct P-E bond (E = P, As, Sb and Bi).
Herein, the characterization and reactivity of the metalated arsinidenyl (SIDipp)AsK (1 a) is described. This compound was obtained via deprotonation of the saturated “parent arsinidene” (SIDipp)AsH (1) with the strong base benzyl potassium and appears as pyrophoric, insoluble, red solid. The ability of crown ethers to improve the solubility of metal compounds through complex formation has been used to obtain crystals of (SIDipp)AsK. Thus, the crown ether complex [K(18‐crown‐6)(SIDipp)As] (1 b) was characterized as the first of its kind by single crystal x‐ray diffraction. Furthermore, (SIDipp)AsK was treated with di‐tert‐butylchloropnictogens (tBu2ECl, E=P, As, Sb, Bi) to give the interpnictogen compounds of the type (SIDipp)AsEtBu2 (2–5) with low valent arsenic substituents.
The behavior of the N‐heterocyclic carbene (NHC) stabilized ‘parent’ phosphinidene [(sIDipp)PH] (Dipp=2,6‐di‐isopropylphenyl) towards 3d‐metal(II) hexamethyldisilazanides is described. This leads to formation of the three‐coordinated phosphinidene adducts [M{PH(sIDipp)}{N(SiMe3)2}2] (M=Mn−Co), as evidenced by X‐Ray diffraction analysis. In solution, all compounds exhibit strong paramagnetism that limited NMR spectroscopic examinations to cobalt. Here it shows that the system is coordinatively highly fluxional, which is mitigtated upon cooling. At low temperatures, small amounts of free phosphinidene becomes further evident by 31P NMR spectroscopy that implicates in part ligand coordination competes with [M{N(SiMe3)2}2] dimerisation and an overall weak binding of the phosphinidene ligand. The rapid chemical exchange is evidenced in the presence of an excess of phosphinidene or a phosphine (PCy3), whereas diethyl ether proved as a stronger donor ligand.
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