Fine-tuned characterization at the solid/solution interface of organotin compounds grafted onto cross-linked polystyrene by using high-resolution MAS NMR spectroscopy.
The structural characterization of organotin compounds that are grafted onto insoluble cross-linked polymers has necessarily been limited to elemental analysis, infrared spectroscopy, and in a few instances, solid-state NMR spectroscopy. This important bottleneck in the development of such grafted systems has been addressed by using high-resolution magic angle spinning (hr-MAS) NMR spectroscopy. The great potential of this technique is demonstrated through the structural characterization of diphenylbutyl-(3,4) and dichlorobutylstannanes (5,6), grafted onto divinylbenzene cross-linked polystyrene by means of a suitable linker (1, 2). First, conditions suitable for the application of hr-MAS NMR spectroscopy were identified by characterizing the (1)H resonance line widths of the grafted organotin moiety following swelling of the functionalized beads in eight representative solvents. The presence of clearly identifiable tin coupling patterns in both the 1D (13)C and 2D (1)H-(13)C HSQC spectra, and the incorporation of (119)Sn chemical shift and connectivity information from hr-MAS 1D (119)Sn and 2D (1)H-(119)Sn HMQC spectra, provide an unprecedented level of characterization of grafted organotins directly at the solid/liquid interface. In addition, the use of hr-MAS (119)Sn NMR for reaction monitoring, impurity detection, and quantification and assessment of the extent of coordination reveals its promise as a novel tool for the investigation of polymer-grafted organotin compounds. The approach described here should be sufficiently general for extension to a variety of other nuclei of interest in polymer-supported organometallic chemistry.
High resolution NMR Centre, Vrije Universiteit Brussel Pleinlaan 2, 1050 Brussels, Belgium.
José C
JC
Martins
Frédéric A G
FA
Mercier
Alexander
A
Vandervelden
Monique
M
Biesemans
Jean-Michel
JM
Wieruszeski
Eberhard
E
Humpfer
Rudolph
R
Willem
Guy
G
Lippens
D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008968:Molecular Conformation; D015394:Molecular Structure; D009947:Organotin Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011137:Polystyrenes; D012996:Solutions
D009947:Organotin Compounds; D011137:Polystyrenes; D012996:Solutions