Koordinationschemie von Aluminium, Gallium und Indium an Übergangsmetallen

Abstract

Der aktuelle Aufschwung der elementorganischen Chemie der Metalle der 13. Gruppe (Erdmetalle) ist nicht zuletzt auf die Etablierung der Koordinationschemie von RaE‐Fragmenten (E=Al, Ga, In; a=1, 2) an d‐Metallen (M) zurückzuführen. In jüngster Zeit bereicherte die Verfügbarkeit niedervalenter Organoelementverbindungen als Synthesebausteine die Strukturchemie dieser Substanzklasse beträchtlich. Diskutiert werden die M‐E‐Bindungsverhältnisse und die Frage nach der Bedeutung von M(dπ)‐E(pπ)‐Rückbindungen sowie potentielle materialwissenschaftliche Anwendungmöglichkeiten, z. B. als Einkomponentenquellen für die Abscheidung dünner intermetallischer Filme nach dem Verfahren der Chemischen Dampfabscheidung.

The reaction of the group-13 alkyls ER3 (E=Al, Ga, In; R=CH2t-Bu, CH2 SiMe3) with the platinum-complex [(dcpe)Pt(H)(CH2t-Bu)]

“…This renewed interest in that chemistry was initiated by the availability of stable low valent, carbenelike compounds E I R (E = Al, Ga, In; R = Cp * , C(SiMe 3 ) 3 , etc. ), pioneered by H. Schnö ckel, W. Uhl and others which opened a new field of group-13 transition metal coordination chemistry [4,9]. The new ''metallic'' ligands E I R (in metaphoric contrast to typical ''none-metallic'' ligands such as phosphanes) revealed a coordination chemistry similar to CO and phosphanes PR 3 .…”

“…The original motivation of these studies arose from the idea to use such mixed metal compounds as ''single-source'' precursors for intermetallic materials predominantly using Metal Organic Vapor Deposition [3,4]. But, because of the involatility of 1 and 2, the interest into these type of Pt-E compounds ceased.…”

“…The platinum group-13 metal chemistry is somewhat unique in the sense, that it allows a quite comprehensive study of the coordination chemistry of both fragments, E I R and E III R 2 at the same transition metal centre. This situation is also nicely illustrated by the existence of the homoleptic complexes [Pt(ER) 4 [11]. Interestingly, it was found, that low coordinated congeners [Ni(AlCp * ) 3 ], which are thought to exist as intermediates in the course of the synthesis of the saturated [Ni(AlCp * ) 4 ], show interesting reactivity and activate aromatic C-H bonds and Si-H bonds, for example [12].…”

“…This situation is also nicely illustrated by the existence of the homoleptic complexes [Pt(ER) 4 [11]. Interestingly, it was found, that low coordinated congeners [Ni(AlCp * ) 3 ], which are thought to exist as intermediates in the course of the synthesis of the saturated [Ni(AlCp * ) 4 ], show interesting reactivity and activate aromatic C-H bonds and Si-H bonds, for example [12]. This kind of transition metal aluminium chemistry holds promise for even more unusual observations, as the structures of [M(AlCp * ) 5 ] (M = Fe, Ru) [13] again turned out to exhibit more complexity as initially thought: Two C-H bonds of the methyl groups of the Cp * -ligands are activated and the coordination sphere around the metal centres contain only three unchanged Al I Cp * ligands besides two Al III centers being linked to M by hydride M-H-Al bridges in addition to M-Al donor acceptor bonds.…”

Halogenation of Lewis acid/base stabilised phosphanylboranes

“…Group 13/15 element compounds play an important role in the design of semiconducting layers as well as for novel inorganic polymers [1]. We are particularly interested in controlled polymerisation processes of 13/15 element compounds, which are derived from the parent compounds of the formula [H 2 EE 0 H 2 ] (E = P, As; E 0 = B, Al, Ga).…”