Structural characterization of poly[(1,2-dimethoxyethane)phosphidolithium]: Parent of the lithium diorganophosphides

Abstract

The structure of [Li(DME)PH2]" in the solid state consists of an infinite polymer of alternating Li and P atoms. The vertices of the chain are four-coordinate, distorted-tetrahedral lithium atoms that are bonded to two P atoms and a 1,2-dimethoxyethane unit. The P atoms are located between each Li vertex such that the Li-P-Li angle is almost linear (176.9 (1)°): Li-P = 2.550 (8), 2.597 (8) Á; Li-O = 2.063 (7), 2.036 (7) A. Crystal data: C4H12P02Li, Mr = 130.05, orthorhombic, P2,212" a = 6.956(2) A, b = 8.773 (1) A, c = 13.455 (2) A, V= 821.1 (5) A3, Dc = 1.052 g cm"3, Z = 4, µ( ) = 2.524 cm'1. Refinement of 451 reflections (/ > 3 (/)) out of 880 unique observed reflections (3°< 26 < 50°) gave R and 7?w values of 0.0591 and 0.0645, respectively.

Lithium, Sodium, and Copper(I) Supersilylphosphanediides M2PSitBu3: Compounds with Novel Spherical (M2P)n Frameworks

“…Structures: Previous structure investigations have shown that monolithium phosphanides MPHR 1 and MPR 2 2 display -M-P-M-P-chains of linked MP groups [6,7] (e. g. polymeric LiPH 2´D ME, LiPHMe´DME, LiPPh 2´2 THF; DME MeOCH 2 CH 2 OMe; for more complex structures of lithium and sodium phosphanides see ref. [8]).…”

“…As expected, the repulsive forces remain small between ions of equivalent charge in chains with alternate cationic and anionic members. The chains in question can combine to give double chains [6,9] (ladder structures; e. g. hexameric LiP(SiMe 3 ) 2 ) or rings [6, 10±12] (e. g. 3 LiP(SiiPr 3 ) 2´L iPH(SiiPr 3 ); see also 1 a, 1 b); in addition, they exist in a separated form as monomers [6,13] (e. g. LiP(SiMe 3 ) 2´( Me 2 NCH 2 CH 2 ) 2 NMe). According to preliminary structure investigations by Driess et al, [8,14] the dilithium phosphanediides M 2 PR 3 display spherical frameworks from linked M 2 P groups.…”

Bis(1,2-dimethoxyethan-O,O′)lithium-phosphanid, -arsanid und -chlorid – drei neue Vertreter des Bis(1,2-dimethoxyethan-O,O′)lithium-bromid-Typs

“…[6] die Ergebnisse von Jones u. a. [5] besta È tigen, zusa È tzlich aber die Geometrie der mit 85°stark gewinkelten PH 2 -Gruppe bestimmen. Auch das homologe, pra È parativ ebenfalls gut nutzbare { [7]; s. auch [8,9] …”

From Racemic Primary Aminoalkyl(phosphanyl)ferrocene Complexes to a Lithium–Phosphorus closo Cluster

“…Especially primary silylphosphines with bulky organosilyl groups undergo such reactions affording phosphinediides that form alkali-metal-phosphorus clusters with spherical lithiumphosphorus frames. [10] Lithium phosphanides on the other hand are known as dimers or oligomers with ladder structures, [11] polymeric chains and helices of connected M-P units, [12] as well as more complex aggregates. [13] Herein we present the syntheses of the first two chiral primary aminoalkyl(phosphanyl)ferrocene complexes: 2-(N,N-Dimethylaminomethyl)phosphanylferrocene (1) was obtained as a racemic mixture, and N,N-dimethyl-1-(2-phosphanylferrocenyl)ethylamine (2) with a d.r.…”