Issue 39, 2022

Coordination chemistry and structural rearrangements of the Me2PCH2AlMe2 ambiphilic ligand

Abstract

Reaction of 2 equivalents of (Me2PCH2AlMe2)2 with [{RhCl(cod)}2] (cod = 1,5-cyclooctadiene) afforded [{κ2P,P-(Me3Al)ClMeAl(CH2PMe2)2}Rh(cod)] (1), which features a κ2-coordinated bis(phosphino)aluminate anion. In compound 1, an Al–Cl substituent bridges to a molecule of AlMe3, which could be removed in vacuo to provide [{κ2P,P-ClMeAl(CH2PMe2)2}Rh(cod)] (2). By contrast, reaction of 1 equiv. of (Me2PCH2AlMe2)2 with [{RhCl(cod)}2] yielded [Rh(cod)(μ-Cl)(Me2PCH2AlMe2)] (3) as the major product, where the phosphine donor of an intact Me2PCH2AlMe2 ligand is coordinated to rhodium and a chloride ligand bridges between Rh and Al. [Rh(cod)(μ-Cl)(Me2PCH2AlClMe)] (3A) and 2 were also formed as minor products. The aforementioned reactions were carried out in benzene or toluene, whereas the 1 : 1 reaction of (Me2PCH2AlMe2)2 with [{RhCl(cod)}2] in THF afforded [{Rh(μ-CH2PMe2)(cod)}2] (4). Reactions of (Me2PCH2AlMe2)2 with iridium(I), gold(I) and platinum(II) precursors were also explored. A 1 : 1 reaction of (Me2PCH2AlMe2)2 with [{IrCl(cod)}2] afforded [{κ2P,P-Cl2Al(CH2PMe2)2}Ir(cod)] (5) as one of two major phosphine-containing products; unlike 3, this compound features two chlorine substituents on aluminium. For comparison, the rhodium analogue of 5, [{κ2P,P-Cl2Al(CH2PMe2)2}Rh(cod)] (6), was also synthesized via the 1 : 1 reaction of {ClAl(CH2PMe2)2}2 with [{RhCl(cod)}2]. Reactions of (Me2PCH2AlMe2)2 with [AuCl(CO)] or [PtCl2(cod)] also resulted in chloride–methyl group exchange between the transition metal and aluminium. However, these reactions generated free (Me2PCH2AlClMe)2 accompanied by gold and ethane, or [PtMe2(cod)], respectively. Reaction of 1.5 equivalents of (Me2PCH2AlMe2)2 with [PtMe2(cod)] at 75 °C afforded zwitterionic [(PtMe{μ-κ1P2P,P-MeAl(CH2PMe2)3})2] (7) which features two tris(phosphino)aluminate anions bridging between PtMe units. Compounds 1–2, 3/3A, 4–7 and (Me2PCH2AlClMe)2 were crystallographically characterized.

Graphical abstract: Coordination chemistry and structural rearrangements of the Me2PCH2AlMe2 ambiphilic ligand

Supplementary files

Article information

Article type
Paper
Submitted
03 Leq 2022
Accepted
13 Way 2022
First published
16 Way 2022

Dalton Trans., 2022,51, 15040-15048

Coordination chemistry and structural rearrangements of the Me2PCH2AlMe2 ambiphilic ligand

K. Paskaruk, D. J. H. Emslie and J. F. Britten, Dalton Trans., 2022, 51, 15040 DOI: 10.1039/D2DT02519A

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