title: A family of rhodium and iridium complexes with semirigid benzylsilyl phosphines: from bidentate to tetradentate coordination modes.
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)]2with the bisbenzylsilanephosphine PhP{(o-C6H4CH2)SiMe2H}2leads 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)]2with 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.
authors.affiliation: Centro de Investigaciones Químicas, Instituto de Investigación en Ciencias Básicas y Aplicadas, Universidad Autónoma del Estado de Morelos, Avenida Universidad 1001, Col. Chamilpa, Cuernavaca, Morelos C. P. 62209, México. vmontielp@uaem.mx.
authors.forename: María Vicky
authors.initials: MV
authors.lastname: Corona-González
authors.forename: Julio
authors.initials: J
authors.lastname: Zamora-Moreno
authors.forename: Cynthia A
authors.initials: CA
authors.lastname: Cuevas-Chávez
authors.forename: Ernesto
authors.initials: E
authors.lastname: Rufino-Felipe
authors.forename: Emmanuelle
authors.initials: E
authors.lastname: Mothes-Martin
authors.forename: Yannick
authors.initials: Y
authors.lastname: Coppel
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Muñoz-Hernández
authors.forename: Laure
authors.initials: L
authors.lastname: Vendier
authors.forename: Marcos
authors.initials: M
authors.lastname: Flores-Alamo
authors.forename: Mary
authors.initials: M
authors.lastname: Grellier
authors.forename: Sylviane
authors.initials: S
authors.lastname: Sabo-Etienne
authors.forename: Virginia
authors.initials: V
authors.lastname: Montiel-Palma