Metal complexes of selenophosphinates from reactions with (R2PSe)2Se: [M(R2PSe2)n] (M = ZnII, CdII, PbII, InIII, GaIII, CuI, BiIII, NiII; R = iPr, Ph) and [MoV2O2Se2(Se2PiPr2)2]

Abstract

The reactions of bis(dialkylselenophosphinyl)selenide with a series of metals have been investigated: synthesis of several metal selenophosphinate complexes and their structures are reported.

Increasing the Lability of Polarised Phosphorus–Phosphorus Bonds

“…[7] The P2-Se1/Se2 bond lengths of 2.193(1) and 2.135(1) Å differ perceptibly, but their average comes close to the mean P-Se distance in ionic diselenophosphinates (2.17 Ϯ 0.03 Å [8] ), and the asymmetry in the PSe 2 moiety resembles that in the η 1 -bound ligands in a complex [Ga(η 2 -Se 2 PiPr 2 )(η 1 -Se 2 PiPr 2 ) 2 ]. [9] The P1-Se1 bond [2.766(1) Å] clearly exceeds a normal single bond in compounds RRЈP-SeRЈЈ (mean distance 2.26 Ϯ 0.07 Å [8] ) but matches the appropriate "inter-ionic" distances (2.64- [10] In contrast to this species, the molecular structure of which was deemed to resemble the "frozen transition state" for a [1,3]-sigmatropic shift of an iminophosphenium fragment between the two selenium atoms of a covalent diselenophosphinate, [10] the P1-Se2 distance in 2 [3.391(1) Å] is clearly nonbonding. Altogether, the molecular structure of 2 ( Figure 1) is best described as contact ion pair of a 1,3,2-diazaphospholenium cation and a η 1 -bound diselenophosphinate anion.…”

Syntheses and crystal structures of the homoleptic [Et4N][M(SC6H4Me-p)4] (M=Ga, In) and [Et4N][Ga(SePh)4]

“…Similarly, the In -S bond lengths in 2 range from [21], but slightly shorter that those in [Ga(Se 2 P i Pr 2 ) 2 (g-Se 2 P i Pr 2 ) 2 ] (av. 2.4200(4) Å) with chelating GaSe 2 bite angle [22].…”

Using coordination chemistry to develop new routes to semiconductor and other materials

“…3). During the reaction, one P-Se bond is broken within ( i Pr 2 PSe) 2 Se and this moiety then acts as a source of dialkylselenophosphinate (R 2 PSe 2 ) − [49]. All the compounds are obtained in good yields as crystalline solids by recrystallization from organic solvents.…”

“…Ternary metal chalcogenides such as CuInSe 2 have been focus of much recent research due to their use in high efficiency, radiation hard, solar cells. They also have a significant fabrication advantage over III-V semiconductors for solar cell applications, since polycrystalline films may be used, as opposed to epitaxial crystal films [49].…”