In(InTrip₂)₃: ein neuartiger In₄‐Cluster mit kurzen In‐In‐Bindungen und trigonal‐planarer Geometrie

Abstract

Trigonal‐planar umgeben ist das Indiumzentrum in In(InTrip2)3 1 (Trip = 2, 4, 6‐iPr3C6H2), dem ersten Indan mit drei außergewöhnlich kurzen Bindungen zu Indanylsubstituenten. Die Verbindung wird durch Reduktion des Diindans Trip2 In‐ InTrip2 mit Lithium erhalten. Im Gegensatz dazu reagieren die Aluminium‐ und Galliumanaloga zu (Trip2M…MTrip2)−‐Ionen, deren M‐M‐Bindung eine π‐Bindungsordnung von 0.5 aufweist.

Dimerization of Indanediyl Fragments: An Alkene Analogue for Group 13?

“…The InIn distance in 6 also lies well above the range established for typical InIn single bonds, such as those within the β‐diketiminato disproportionation product [{{HC[CMeN(dipp)] 2 }InCl} 2 ] (2.8343(7) Å) and the three‐coordinate indium centers of [{(2,4,6‐ i Pr 3 C 6 H 2 ) 2 In} 2 ] (2.775(2) Å), both of which feature formally divalent indium 24. 25 The β‐diketiminato chelate structure is effectively planar (root‐mean‐square deviation of the In‐N1‐C1‐C2‐C3‐N2 plane: 0.03 Å) with the result that the trans ‐bent configuration may be accurately defined by the In′‐In‐C2 angle of 113.02°. This represents an out‐of‐plane angle of 66.98° and indicates that dimerization occurs with a significantly greater degree of pyramidalization (with respect to a planar alkene‐like D 2 h structure) than that observed in the majority of homoleptic stannylenes of the general formula R 2 SnSnR 2 (typically δ =30–45°) 1…”

[In3(In2)3(PhP)4(Ph2P2)3Cl7(PEt3)3]- A New Molecular III/V Compound Featuring an Unusual 19-Atom Cage

“…The In À P distances range between 253.3 and 261.6 pm, the InÀIn bonds are 274.1 pm on average. These values correspond well to analogous bonds occurring in other In/P compounds; for example, in [{(tBu 2 P) 2 InCl} 2 ] or [MesInPMes] 4 (Mes 2,4,6-Me 3 C 6 H 2 ) the InÀP bonds range between 258.2 and 266.0 pm [1±3] and in [Trip 4 In 2 ] (Trip 2,4,6-iPr 3 C 6 H 2 ) [9] or [In 2 I 4 (nPr 3 P) 2 ] [10] the In À In single bonds are 277.5 and 274.5 pm, respectively. In contrast, longer InÀIn distances of disordered solvent molecules (Et 2 O), but which cannot be unambiguously assigned.…”

A Novel Soluble InI Precursor for Pn Ligand Coordination Chemistry

“…Compared to 10 , significantly shorter InIn distances (2.887(2)–3.18(2) Å) are found in tetrahedral In 4 clusters synthesized in the groups of Uhl, Cowley, and Linti, which definitely show In I In I interactions 1a,g. 26 Even shorter InIn distances (2.696(2) Å) are reported for a trigonal‐planar In 4 cluster by Power et al 27. However, in the compounds [InC 5 R 5 ] (R=H, Me) the intermetallic distances (3.942(1)–3.986(1) Å) are considerably longer than those in 10 28.…”

“…Its 19 F NMR spectrum in CD 2 Cl 2 at room temperature shows a singlet at d = À75.6 ppm, which is in agreement with the 36 chemically equivalent fluorine atoms of the anion. The 27 Al NMR spectrum in CD 2 Cl 2 at room temperature exhibits a singlet at d = 33.7 ppm. In the ESI mass spectrum in CH 3 CN signals for naked In…”