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Issue 27, 2017
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A family of rhodium and iridium complexes with semirigid benzylsilyl phosphines: from bidentate to tetradentate coordination modes

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Abstract

The synthesis of a new trisbenzylsilanephosphine P{(o-C6H4CH2)SiMe2H}3 (1) is shown to proceed with high yields from P(o-tolyl)3. Compound 1 coordinates to the Rh and Ir dimers [MCl(COD)]2 (M = Rh, Ir) in a tetradentate or tridentate fashion, depending on the strict exclusion of water. The dimeric compounds [ClM(SiMe2CH2-o-C6H4)2P(o-C6H4-CH2SiMe2H)]2, 2Rh and 2Ir, feature a tetradentate coordination of the starting ligand with P and two Si atoms as well as a non-classical agostic Si–H group. The presence of adventitious water in the solvents leads to the formation of two new complexes [(μ2-Cl)2M2(SiMe2CH2-o-C6H4)2P(o-C6H4-CH2SiMe2OSiMe2CH2-o-C6H4–)P(SiMe2CH2-o-C6H4)2], 3Rh and 3Ir, which feature a siloxane bridge through Si–H bond breaking in 2. Reaction of [RhCl(COD)]2 with the bisbenzylsilanephosphine PhP{(o-C6H4CH2)SiMe2H}2 leads to the formation of compound 4Rh which features also a dimeric structure with the SiPSi ligand coordinated through the two silicon atoms, one of which occupies the apical position of a square-pyramidal geometry in the solid state, while the second is disposed equatorially trans to π-donor Cl. Finally, bidentate coordination of a PSi ligand is achieved by reaction of [RhCl(COD)]2 with Ph2P{(o-C6H4CH2)SiMe2H} which leads to the monometallic species [RhCl(SiMe2CH2-o-C6H4-PPh2)2], 5Rh, incorporating two chelating PSi ligands and maintaining a Cl ligand.

Graphical abstract: A family of rhodium and iridium complexes with semirigid benzylsilyl phosphines: from bidentate to tetradentate coordination modes

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Publication details

The article was received on 27 Feb 2017, accepted on 31 Mar 2017 and first published on 07 Apr 2017


Article type: Paper
DOI: 10.1039/C7DT00727B
Citation: Dalton Trans., 2017,46, 8827-8838
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    A family of rhodium and iridium complexes with semirigid benzylsilyl phosphines: from bidentate to tetradentate coordination modes

    M. V. Corona-González, J. Zamora-Moreno, C. A. Cuevas-Chávez, E. Rufino-Felipe, E. Mothes-Martin, Y. Coppel, M. A. Muñoz-Hernández, L. Vendier, M. Flores-Alamo, M. Grellier, S. Sabo-Etienne and V. Montiel-Palma, Dalton Trans., 2017, 46, 8827
    DOI: 10.1039/C7DT00727B

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