Transition-Metal-Substituted Alanes: Synthesis and Spectroscopic Studies and the Structure of (η5-C5H5)(CO)2Fe-Al[(CH2)3NMe2](iBu)

Roland A. Fischer, Thomas Priermeier

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Abstract

Salt elimination between X-Al[(CH2)3NMe2](R) and Y-A1(X)2(Do) (X, Y = H, Cl, Br; R = Cl, Br, iBu, CH2tBu; Do = NMe3, quinuclidine, THF) and [L(CO)nM][K] (M = Fe, Ru, Co; L = CO, PMe3, η5-C5H5; = 1–3) in THF solution quantitatively gives the transition-metal-substituted alanes L(CO)nM-Al[(CH2)3NMe2](R) (2a-h) and L(CO)nM-Al(X)2(Do) (2k-m). The new compounds were characterized by means of elemental analysis and 1H, 13C, 31P, and 27Al NMR, EI-MS, and infrared v(CO) and v(Al-H) data. 2a-m constitute rare examples of nonbridged direct transition-metal-aluminum bonds. Those bonds are rather polarized in a Feδ--Alδ+ fashion and are thus highly reactive toward cleavage in the course of electrophilic or nucleophilic attack. X-ray single crystal data for 2a, (η5-C5H5)(CO)2-Fe-Al[(CH2)3NMe2](iBu: monoclinic, P21/n, a = 868.0(2) Å, b = 13.468(2) Å, c = 15.213(3)Å, β = 101.79(1)°, V = 1741 Å3, Z = 4, R = 0.0536 (Rw = 0.0483). The σ(Fe-Al) bond length is 2.456(1) Å. 2a-d are used as candidates to generate intermetallic Fe/Al and Co/Al thin films by low-pressure MOCVD.

Original languageEnglish
Pages (from-to)4306-4314
Number of pages9
JournalOrganometallics
Volume13
Issue number11
DOIs
StatePublished - 1 Nov 1994

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