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- Title
From a Diphosphanegermylene to Nickel, Palladium, and Platinum Complexes Containing Germyl PGeP Pincer Ligands.
- Authors
Álvarez‐Rodríguez, Lucía; Brugos, Javier; Cabeza, Javier A.; García‐Álvarez, Pablo; Pérez‐Carreño, Enrique
- Abstract
The PGeP pincer-type germylene Ge(NCH2P tBu2)C6H4 ( 1) has been used to prepare a family of group 10 metal complexes, namely, [MCl{κ3 P, Ge, P-GeCl(NCH2P tBu2)2C6H4}] (M=Ni ( 2Ni), Pd ( 2Pd), Pt ( 2Pt)), 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 2Ni and 2Pd easily led to the hydrolyzed products [Ni2Cl2{μ-(κ3 P, Ge, P-Ge(NCH2P tBu2)2C6H4)2O}], which features a Cl−Ni−Ge−O−Ge−Ni−Cl bond sequence, and [PdCl{κ3 P, Ge, P-Ge(OH)(NCH2P tBu2)2C6H4}], which contains a hydroxidogermyl PGeP pincer ligand ( 2Pt is reluctant to undergo hydrolysis). Simple chloride exchange reactions led to the methoxidogermyl, methylgermyl, and phenylgermyl derivatives [MCl{κ3 P, Ge, P-GeR(NCH2P tBu2)2C6H4}] (M=Pd, Pt; R=OMe, Me, Ph). Whereas the palladium complexes [PdCl{κ3 P, Ge, P-GeR(NCH2P tBu2)2C6H4}] (R=Me, Ph) reacted with more MeLi or PhLi to give palladium black and GeR2(NCH2P tBu2)2C6H4 (R=Me, Ph), similar reactions with the analogous platinum complexes afforded the transmetalation derivatives [PtR{κ3 P, Ge, P-GeR(NCH2P tBu2)2C6H4}] (R=Me, Ph). The short length of the CH2P tBu2 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.
- Subjects
PHOSPHENES; NICKEL compounds; PALLADIUM compounds; PLATINUM compounds; TRANSITION metal complexes
- Publication
Chemistry - A European Journal, 2017, Vol 23, Issue 60, p15107
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201702629