The chameleonic reactivity of dilithio bis(alkylamido)cyclodiphosph(iii)azanes with chlorophosphines

Abstract

To synthesize a bis(diphosphinylamine) ligand for use in late-metal catalysis dilithio bis(tert-butylamido)cyclodiphosph(iii)azane was treated with two equivalents of (Ph)2PCl. The chlorodiphenylphosphine attacked the dilithium salt kinetically at phosphorus, followed by a rearrangement to an unsymmetrical P, N-di-substituted product. Solid-state structures of both products were determined, and the activation energy for the rearrangement was measured. To gain further insight into the location of chlorophosphine attack (N versus P) on lithium diamides, dilithio bis(cyclohexylamido)cyclodiphosph(iii)azane or dilithio bis(tert-butylamido)cyclodisilazane was treated with two equivalents of PCl3. In each case only the symmetrically N,N'-substituted bis(PCl2) product was obtained and characterized by X-ray analysis. The structures of these latter compounds are unusual, because in both cases a bicyclic compound with a bis(amido) chelated, central P-Cl moiety was expected based on precedent. The two proximal and juxtaposed PCl2 groups may provide a starting point for potentially novel reactivity studies.

Synthesis of a Molecule with Five Different Adjacent Pnictogens

“…There are a lot of diazadiphosphetidines described in the literature with a wide range of different substitution patterns but only a few with antimony or bismuth moieties like in (PNR 1 ) 2 (NR 1 ) 2 PnR 2 (Pn=Sb: R 1 = t Bu, Ph; R 2 =Cl, N 3 , OPh, N(tms) 2 ; Pn=Bi R 1 = t Bu; R 2 =Cl) . Worth mentioning are also some mixed diazapnictitidines by A. Schulz et al.…”

Main Group Molecular Switches with Swivel Bifurcated to Trifurcated Hydrogen Bond Mode of Action

“…Among the molecular motifs comprising P–N bonds, P 2 N 2 cyclodiphosphazane building blocks are capable of forming a broad range of cyclic and acyclic frameworks. These main group systems have shown to be excellent ligands for metal coordination − and versatile modular building blocks for the construction of larger molecules for biological applications and supramolecular chemistry. − …”

Synergic Topological- and Size-Control on Phosphazane Chemistry: First Unfolded Hybrid Tetrameric Macrocycle

“…[1][2][3][4] In this context, cyclodiphosphazane-based inorganic macrocycles have drawn attention due to both their promise in host guest chemistry and anion sensing. [5][6][7][8][9][10][11][12][13][14] Cyclophosphazane species have been widely explored over the past decades due to their chemical versatility, [15] action as excellent neutral and/or anionic ligands for metal coordination [16][17][18][19][20][21][22][23] and building blocks for the construction of larger molecules, as well as utility in biological applications and supramolecular chemistry. [12,13,[24][25][26][27][28][29][30][31][32] Depending on the nature of the bifunctional linkers employed, their reaction with dichlorocyclodiphosphazane, [ClP(μ-N t Bu)] 2 (1), yields differently-sized fully inorganic or hybrid macrocycles.…”