Inorganic Chemistry, Vol.50, No.5, 1931-1941, 2011
Immobilized Boron-Centered Heteroscorpionates: Heterocycle Metathesis and Coordination Chemistry
The preparation of a resin-supported boron-scorpionate ligand and its nickel(II) coordination complexes are reported. The supported ligand is prepared as its potassium salt, making it a general reagent suitable for chelation of any transition metal ion. Resin-immobilized benzotriazole (Bead-btz) reacted cleanly with KTp(star) (Tp(star) = hydrotris(3,5dimethylpyrazolyl)borate) by heterocycle metathesis in warm dimethylformamide (DMF) to yield bead-Tp'K, {resin-btz(H)B(pz(star))(2)}K. Significantly, bead-Tp'K readily bound nickel(II) from simple salts with minimal leaching of the nickel ion. Bead-Tp'NiNO3 reacts further with cysteine thiolate (ethyl ester), imparting the deep green color to the beads characteristic of a Tp(R)NiCysEt coordination sphere. Bead-Tp'NiCysEt exhibited an oxygen sensitivity similar to Tp(star)NiCysEt in solution (Inorg. Chem. 1999, p 5690) and also independently verified for a selenocystamine analogue, Tp(star)NiSeCysAm. Addition of fresh cysteine thiolate ethyl ester to oxidized bead-Tp'NiCysEt reproduced the original green color. Heterocycle metathesis was also used to prepare KTp' as a white solid. Reaction with nickel(II) gave (Tp')(2)Ni, separable into two different isomers. The air-sensitive molybdenum(0) complex, [PPh4][Tp'Mo(CO)(3)], was also prepared and the C, complex symmetry demonstrated by infrared and C-13 NMR spectroscopies. Immobilized TpmMo(CO)(3) was prepared from the previously reported resin-supported tris(pyrazolyl)methane. In contrast to its weak coordination of nickel(II) (Inorg. Chem. 2009, p 3535), bead-Tpm proved a strong chelate toward this second row metal. The supported scorpionates described here should find use in studies of selective metal-protein binding, metalloprotein modeling, and heterogeneous catalysis, and render such scorpionate applications amenable to combinatorial methods.