Reactions of Neopentylindium(III) Derivatives with Isopropylphosphorus Compounds

Abstract

A 1:1 mixture of In(CH2CMe3)3 and HP(i-Pr)2 at room temperature undergoes a very slow hydrocarbon elimination reaction to form [(Me3CCH2)2InP(i-Pr)2]2 and neopentane. The indium phosphide [(Me3CCH2)2InP(i-Pr)2]2 has also been prepared by reacting KIn(CH2CMe3)3H with ClP(i-Pr)2 in pentane. When pentane solutions of these reagents were combined at −78 °C and then maintained at ∼20 °C for 2 days, [(Me3CCH2)2InP(i-Pr)2]2, (Me3CCH2)3In·P(H)(i-Pr)2, (Me3CCH2)3In·P2(i-Pr)4, (Me3CCH2)3In·P(CH2CMe3)(i-Pr)2, H2, indium metal, and KCl were observed. The formation of all products is explained by a set of experimentally verified reactions. An X-ray structural study of [(Me3CCH2)2InP(i-Pr)2]2 shows each molecule to have an unusual puckered four-membered In2P2 core.

π-Bonding and the Lone Pair Effect in Multiple Bonds Involving Heavier Main Group Elements: Developments in the New Millennium

“…17 kcal mol -1 , tends to bear out this view. 124 Calculations on parent mono-, di-, and triamidoborane, alane, gallane, and indane and their silyl substituted congeners provided similar M-N bond lengths and showed that, although π-bonding plays a significant role in the structures of amido boranes, it is weak in the heavier group 13 congeners. The calculations also showed that negative hyperconjugative interactions are significant when the amido groups are rotated out of the metal coordination plane.…”

“…Its structure may be compared with the behavior of TlN(SiMe 3 ) 2 , which has a dimeric structure in which two Tl + ions symmetrically bridge two N(SiMe 3 ) 2 ligands in the solid state but was shown by gas electron diffraction (ged) to have a monomeric structure in the vapor phase. 124 The corresponding structurally characterized group 13 element derivatives of the heavier pnictogens are given in Table 7. 108,[125][126][127][128][129][130][131][132][133][134][135][136][137] Most derivatives involve bonding to phosphorus.…”

Bis(μ-diethylphosphido-κ2P:P)bis[bis(2,4,6-trimethylphenyl)indium(III)]

“…For related dimeric phosphanylindanes, see: Alcock et al (1989); Wells et al (1992); Aitchison et al (1989); Beachley et al (1987Beachley et al ( , 1993Beachley et al ( , 1995Beachley et al ( , 2001; Culp et al (1997); Malik et al (1996); Thomas et al (2002); Wells et al (1993); von Hanisch (2001). For related trimeric phosphanylindanes, see: Burns et al (1994); Werner & Neumü ller (1996); Banks et al (1991).…”

“…Phosphanylindanes [R 2 InPR′ 2 ] n form dimeric or trimeric structures in the solid state via intermolecular In-P coordinate bonding interactions (Beachley et al, 2001;Werner & Neumuller 1996). Dimeric structures feature distorted tetrahedral geometries at indium and phosphorus, and planar four-membered In 2 P 2 ring cores.…”