Issue 42, 2009
From the journal:

Dalton Transactions

Synthesis and reactivity of diphosphine metal complexes bearing peripheral ketenimine functionalities†

Javier Ruiz,*a   Marta P. Gonzalo,a   Marilín Vivanco,a   Roberto Quesadab  and  Marta E. G. Mosquerac  

* Corresponding authors

a Departamento de Química Orgánica e Inorgánica, Facultad de Química, Universidad de Oviedo, Oviedo, Spain
E-mail: jruiz@uniovi.es
Fax: (+34) 985103446

b Departamento de Química, Facultad de Ciencias, Universidad de Burgos, Burgos, Spain

c Departamento de Química Inorgánica, Universidad de Alcalá, Alcalá de Henares, Spain

Abstract

Diphosphinoketenimine ligands (PPh2)2C[double bond, length as m-dash]C[double bond, length as m-dash]NR (1a R = tBu, 1b R = Ph) were reacted with different Cu(I), Ag(I), Au(I), Pd(II), Ru(II) and Mo(0) metal complexes bearing weakly coordinating ligands yielding a number of mono-, di-, and trimetallic species with the diphosphine acting as either chelate or bridging ligand. The reactivity of some of the new complexes toward water and MeLi was investigated. The mononuclear Pd(II) complex [PdCl2{(PPh2)2C[double bond, length as m-dash]C[double bond, length as m-dash]NPh}] (6b) is transformed into the diphosphinoamide complex [PdCl2{(PPh2)2CHC([double bond, length as m-dash]O)(NHPh)}] (12) by nucleophilic addition of water. Similarly, treatment of 6b with MeLi yields the diphosphinoenamine complex [PdCl2{(PPh2)2C[double bond, length as m-dash]C(Me)(NHPh)}] (14). A different behaviour is observed in the treatment of diphosphinoketenimine with water in the presence of Cu(I) ion, which leads to hydrolysis of the ligand involving P–C bond cleavage, underscoring the influence of the coordination environment in the reactivity showed by the coordinated ligand. The liberation of the metal assisted synthesized diphosphines from the Pd(II) metal center can be achieved easily and in quantitative yields by treatment with aqueous KCN solution.

Graphical abstract: Synthesis and reactivity of diphosphine metal complexes bearing peripheral ketenimine functionalities

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Article information

DOI
https://doi.org/10.1039/B903375K
Article type
Paper
Submitted
18 Feb 2009
Accepted
11 Sep 2009
First published
02 Oct 2009

Dalton Trans., 2009, 9280-9290

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Synthesis and reactivity of diphosphine metal complexes bearing peripheral ketenimine functionalities

J. Ruiz, M. P. Gonzalo, M. Vivanco, R. Quesada and M. E. G. Mosquera, Dalton Trans., 2009, 9280 DOI: 10.1039/B903375K

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