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Synthesis and structure of novel [Ph(RO)PSe2]- complexes
Ian P Gray1, Alexandra M Z Slawin, J Derek Woollins
1School of Chemistry, University of St Andrews, St Andrews, Fife, UK KY16 9ST.
Dalton Transactions (Cambridge, England : 2003)
|June 16, 2005
Summary
New phosphonodiselenoato anions, [Ph(RO)PSe2]-, were synthesized and complexed with metals. Structural characterization revealed diverse coordination geometries in nickel, cadmium, and lead complexes, including novel dimeric lead structures.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Materials Science
Background:
- Woollins reagent, (PhPSe2)2, is a versatile precursor for selenium-containing ligands.
- Non-symmetric phosphonodiselenoato anions offer unique coordination possibilities.
Purpose of the Study:
- To synthesize and characterize novel phosphonodiselenoato anions and their metal complexes.
- To investigate the structural diversity of these complexes with various metals.
- To explore new structural motifs, particularly in lead complexes.
Main Methods:
- Reaction of Woollins reagent with sodium alkoxides (NaOR) to form anions.
- Complexation of anions with nickel, cadmium, and lead.
- Characterization using multinuclear NMR (31P, 1H, 13C), IR, and mass spectrometry.
- X-ray crystallography for structural determination.
Main Results:
- Synthesis of non-symmetric phosphonodiselenoato anions [Ph(RO)PSe2]-.
- Nickel complex Ni[Ph(MeO)PSe2]2 exhibits a square-planar ML2 structure.
- Cadmium complex Cd[Ph(MeO)PSe2]2 shows a dimeric M2L4 structure.
- Two distinct lead complexes were identified, including a novel dimeric structure with a central Pb2Se2 ring.
Conclusions:
- The phosphonodiselenoato ligand provides access to diverse metal complex structures.
- Novel coordination environments and dimeric structures were achieved, especially with lead.
- The study expands the library of selenium-containing coordination compounds and their structural possibilities.