A new approach to coordination chemistry involving phosphorus-selenium based ligands. Ring opening, deselenation and phosphorus-phosphorus coupling of Woollins’ Reagent |
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| Authors: | Richard CS Wong Mei Lee Ooi |
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| Institution: | Department of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia |
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| Abstract: | The facile reaction of CpCr(CO)3]2 (1) with an equivalent of 2,4-bis(phenyl)-1,3-diselenadiphosphetane-2,4-diselenide or Woollins’ Reagent (WR) at ambient temperature gave mainly CpCr(CO)2]2Se (3) as the main product. A similar reaction with an excess of 1 gave 3 (58%) and trans-CpCr(CO)2(SePPh)]2 (5, 25%). However reaction with an equivalent of the triply bonded congener Cp2Cr2(CO)4 (2) at 60 °C took 3 h to complete and led to the isolation of trans-CpCr(CO)2(SePPh)]2 (5, 3%), CpCr(CO)2(SeP(H)Ph) (4, 18%) and CpCr(Se2P(O)Ph)]2 (6, 2%). The ring-opening reaction of WR via an initial homolytic P-Se bond cleavage by CpCr(CO)n· (n = 2 (2A) or 3 (1A)) depicts a new approach to coordination chemistry involving P-Se based ligands. A mechanistic pathway was proposed according to the evidences obtained from thermolysis, NMR and mass spectra studies. All the products of 4, 5 and 6 have been structurally characterized by single-crystal X-ray diffraction analysis. |
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| Keywords: | Woollins&rsquo Reagent Congener Ring-opening Bond cleavage Mechanistic pathway Thermolytic studies |
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