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From a Diphosphanegermylene to Nickel, Palladium, and Platinum Complexes Containing Germyl PGeP Pincer Ligands

DOIFull Paper Access

37

Citations

62

References

2017

Year

Lucía Álvarez‐Rodríguez, Javier Brugos, Javier A. Cabeza, Pablo García‐Álvarez, Enrique Pérez‐Carreño
Chemistry - A European Journal

Abstract

The PGeP pincer-type germylene Ge(NCH<sub>2</sub> PtBu<sub>2</sub> )C<sub>6</sub> H<sub>4</sub> (1) has been used to prepare a family of group 10 metal complexes, namely, [MCl{κ<sup>3</sup> P,Ge,P-GeCl(NCH<sub>2</sub> PtBu<sub>2</sub> )<sub>2</sub> C<sub>6</sub> H<sub>4</sub> }] (M=Ni (2<sub>Ni</sub> ), Pd (2<sub>Pd</sub> ), Pt (2<sub>Pt</sub> )), featuring a chloridogermyl PGeP pincer ligand and a Cl-Ge-M-Cl bond sequence. Their reactivity is not initially centered on the metal atom but on their Ge atom. Complexes 2<sub>Ni</sub> and 2<sub>Pd</sub> easily led to the hydrolyzed products [Ni<sub>2</sub> Cl<sub>2</sub> {μ-(κ<sup>3</sup> P,Ge,P-Ge(NCH<sub>2</sub> PtBu<sub>2</sub> )<sub>2</sub> C<sub>6</sub> H<sub>4</sub> )<sub>2</sub> O}], which features a Cl-Ni-Ge-O-Ge-Ni-Cl bond sequence, and [PdCl{κ<sup>3</sup> P,Ge,P-Ge(OH)(NCH<sub>2</sub> PtBu<sub>2</sub> )<sub>2</sub> C<sub>6</sub> H<sub>4</sub> }], which contains a hydroxidogermyl PGeP pincer ligand (2<sub>Pt</sub> is reluctant to undergo hydrolysis). Simple chloride exchange reactions led to the methoxidogermyl, methylgermyl, and phenylgermyl derivatives [MCl{κ<sup>3</sup> P,Ge,P-GeR(NCH<sub>2</sub> PtBu<sub>2</sub> )<sub>2</sub> C<sub>6</sub> H<sub>4</sub> }] (M=Pd, Pt; R=OMe, Me, Ph). Whereas the palladium complexes [PdCl{κ<sup>3</sup> P,Ge,P-GeR(NCH<sub>2</sub> PtBu<sub>2</sub> )<sub>2</sub> C<sub>6</sub> H<sub>4</sub> }] (R=Me, Ph) reacted with more MeLi or PhLi to give palladium black and GeR<sub>2</sub> (NCH<sub>2</sub> PtBu<sub>2</sub> )<sub>2</sub> C<sub>6</sub> H<sub>4</sub> (R=Me, Ph), similar reactions with the analogous platinum complexes afforded the transmetalation derivatives [PtR{κ<sup>3</sup> P,Ge,P-GeR(NCH<sub>2</sub> PtBu<sub>2</sub> )<sub>2</sub> C<sub>6</sub> H<sub>4</sub> }] (R=Me, Ph). The short length of the CH<sub>2</sub> PtBu<sub>2</sub> arms of the PGeP pincer ligands forces the metal atoms of all these complexes to be in a very distorted square-planar ligand environment. The reactivity results have been rationalized with theoretical calculations.

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