Rapid Synthesis of a Functional Resin‐Supported Scorpionate and Its Copper(I, II), Rhodium(I), and Chromium(III) Complexes. Issue 15 (26th April 2016)

• Record Type: Journal Article
• Authors: Desrochers, Patrick J.; Pearce, Adam J.; Rogers, T. Ryan; Rodman, Jeremy S.
• Other Names: Pettinari C. guestEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 15/16(2016)
• Page Start: 2465
• Page End: 2473
• Publication Date: 2016-04-26
• Subjects: N ligands -- Scorpionates -- Immobilization -- Microwave chemistry; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201501254
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Boron‐scorpionates are readily prepared by microwave (MW) assisted methods. Such a method is described here, leading to the rapid preparation of a heterogeneous resin‐supported scorpionate as its sodium salt, BdPhTpNa [BdPhTp = phenyltris(1‐pyrazolyl)borate covalently bound through the phenyl ring to commercial cross‐linked polystyrene resin beads]. Formation of a functional heterogeneous scorpionate was confirmed from the subsequent reactions of several metal complexes. This supported ligand system coordinates a variety of transition metal ions including copper(I and II), chromium(III) and rhodium(I). Chromium(III) provided definitive electronic spectral evidence for supported–TpCr III coordination spheres, including reversible ligand‐substitution reactions. The copper(I) case exhibited typical scorpionate Cu I reactivity including spectroscopically characterized (IR and 31 P NMR) complexes with CO, PPh3, and HCCH. Copper(II) provided EPR evidence for heterogeneous scorpionates. The supported rhodium(I) complex was demonstrated to be a recyclable heterogeneous rhodium–scorpionate catalyst. These results all support the conclusion that the immobilized chelate forms coordinatively unsaturated half‐sandwich metal complexes (LM n + ) capable of efficient ligand‐substitution reactions or catalytic activity. Abstract : A microwave‐assisted method is described for the rapid preparation of a heterogeneous resin‐supported scorpionate as its sodium salt. Formation of functional heterogeneous metal scorpionates was confirmed from subsequent reactions of its varied metal (Cr, Cu, Rh) complexes.