Hydrazin‐Addukte mit Dialkylindiumchloriden — Überraschende strukturelle Vielfalt bei einfachen Verbindungen

Abstract

Dialkylindiumchloride reagieren mit Hydrazinderivaten zu unterschiedlichen Addukten, die eine bemerkenswerte strukturelle Vielfalt zeigen. Die äquimolare Umsetzung von Me2InCl mit Phenylhydrazin ergibt das erwartete Monoaddukt [Me2InCl·NH2NHC6H5] (1), in dem der Ligand über sein NH2‐Stickstoffatom an das zentrale Indiumatom koordiniert und das im festen Zustand über eine In—Cl—In‐Brücke dimer vorliegt. Bei der entsprechende Reaktion mit tert‐Butylhydrazin entsteht dagegen unter asymmetrischer Spaltung des Indiumhalogenids die ionische Verbindung [Me2InCl2]‐[Me2In(NH2NHCMe3)2]+ (3), in deren kationischem Bestandteil zwei NH2‐Gruppen am Indiumatom koordinieren. Im Gegensatz dazu ergibt sterisch höher abgeschirmtes (Me3C)2InCl mit diesem Hydrazin ein Addukt 2, das zwar analog zu 1 ist, im Festkörper aber nicht dimerisiert. Ein Unterschuß von Phenylhydrazin führt zur Bildung der Verbindung (Me2InCl)4[NH2N(H)C6H5]2 (4), in der ein Ausschnitt aus der Leiterstruktur von Me2InCl mit vier Formeleinheiten des Halogenids durch zwei terminale Hydrazinliganden stabilisiert wird. Nur in wenigen Kristallen wurde eine entsprechende Verbindung 5 mit tert‐Butylhydrazin erhalten, die eine komplizierte dreidimensionale Struktur aufweist. Daneben wird über die Molekülstruktur von In(CMe3)3 (6) berichtet.

Different Reactivity Patterns in the Reactions of the Homologous Trimethylelement Compounds EMe3 (E = Al, Ga, In) with Methylhydrazine

“…Steric repulsion between the alkyl groups of the hydrazine ligands and the alkyl groups attached to the aluminum or gallium atoms may compensate for the stronger basicity, and usually the coordination occurs through the sterically less shielded NH 2 nitrogen atom. [3][4][5][6][7][8][9] To understand its unusual coordination mode, compound 3 was investigated by quantum chemical methods. The corresponding tri(tert-butyl)gallium methylhydrazine adduct was included in order to test the influence of steric shielding.…”

“…A similar compound was (9), Ga4-N3B 203.0(6), N11-N12 143.6(5), N21-N22 144.5(5), N31-N32 151(2), N3A-N3B 149(1), N11-Ga1-N31 95.2(2), N11-Ga1-N3A 95.1(2), Ga1-N11-Ga2 108.9(2), N11-Ga2-N32 96.5(3), N11-Ga2-N3B 94.3(2), Ga2-N32-Ga4 117.3(4), Ga2-N32-N31 104.7 (7), Ga4-N32-N31 104.6(8), Ga2-N3B-Ga4 117.3(3), Ga2-N3B-N3A 112.7(5), Ga4-N3B-N3A 114.6(5), N32-Ga4-N21 94.2(3), N3B-Ga4-N21 95. 8(2), Ga4-N21-Ga3 107.0(1), N21-Ga3-N31 94.9(2), N21-Ga3-N3A 94.9(2), Ga3-N31-N32 112.3(6), Ga3-N31-Ga1 117.6(4), Ga1-N31-N32 113.6(7), Ga3-N3A-N3B 104.1(5), Ga3-N3A-Ga1 117.0(3), Ga1-N3A-N3B 105.5 (6). obtained by the reaction of trimethylgallium with hydrazine, H 2 N-NH 2 , without reference to the formation of an intermediate adduct.…”

“…[2] Simple adducts between hydrazines and trialkylelement compounds or alkylelement halides resulted from donor-acceptor interactions without secondary reactions. [3][4][5][6][7][8][9] Hydrazides obtained by the release of hydrogen, alkanes, or lithium halides were monomeric in a few cases only owing to steric shielding [10] or through the coordinative saturation of the central atoms by a side-on coordination of the hydrazido group through both nitrogen atoms. [11,12] Most compounds gave dimeric formula units with four-, five-, or six-membered heterocycles and 1,1-(geminal) or 1,2-bridging (vicinal) functions of the N-N bonds.…”

Dimethylindium hydrazides [Me2In-NH-NHR]2 (R=CMe3, C6H5)

“…In contrast to the well-known chemistry of aluminum and gallium hydrazides, only very few reports on indium hydrazides can be found in the literature. One salt-like compound was reported by the group of Nö th [21], some adducts were published by our group [22], and only one neutral indium hydrazide was obtained by Gladfelter with the compound In{N(SiMe 3 )-NMe 2 } 3 [23]. More systematic investigations into the applicability of indium hydrazides for the formation of indium nitride require the availability of a broader spectrum of corresponding compounds possessing different properties such as solubility, volatility or thermal stability.…”

Aluminum, Gallium, and Indium Hydrazides and the Generation of Oligonuclear Element-Nitrogen Cages: Molecular Intermediates on the Way to Element Nitrides

“…24 A unique coordination pattern is observed for the polymeric structure of Me 2 ClInrNH 2 N-(H)CMe 3 in which each nitrogen atom of the neutral hydrazine ligand is coordinated to a metal atom. 24 ' HYDRAZIDES WITH THE MONOANIONIC HYDRAZIDE LIGAND [N(H)N(R 0 )H] À The hydrazine adducts (1 and 2) generally eliminate below room temperature or upon slight warming spontaneously 1 equiv of the corresponding alkane. The products are monoanionic hydrazides, [N(H)N(H)R 0 ] À (eq 2), which in solution and the solid state have dimeric structures with bridging metal atoms.…”