Homo- and heterodinuclear complexes of the tetrakis(pyrazolyl)borate ligand

Abstract

Monometallic complexes of the tetrakis(pyrazolyl)borate ligand [ML(2){B(pz)(4)}] {M = Rh, Ir; L(2) = eta-cod, eta-nbd, (CO)(2), (CO)(PPh(3))} have two free pyrazolyl rings which can be coordinated to a second ML(2) unit to give the dimeric compounds [L(2)M{mu-B(pz)(4)}ML(2)](+), and to a metal halide to give heterobimetallic species [L(2)M{mu-B(pz)(4)}M'Cl(2)]. (1)H NMR spectroscopy shows that [(eta-cod)Rh{mu-B(pz)(4)}Rh(eta-cod)](+) 1(+), [(eta-nbd)Rh{mu-B(pz)(4)}Rh(eta-nbd)](+) 2(+), [(eta-cod)Ir{mu-B(pz)(4)}Ir(eta-cod)](+) 3(+) and [(CO)(2)Rh{mu-B(pz)(4)}Rh(CO)(2)](+) 4(+) are fluxional at room temperature. Cooling a solution of [(eta-cod)Rh{mu-B(pz)(4)}Rh(eta-cod)](+) 1(+) to -90 degrees C slows the fluxional process, which involves inversion of the two B-(N-N)(2)-M six-membered rings. Attempts to synthesise the asymmetric complexes [(eta-cod)Rh{mu-B(pz)(4)}Rh(eta-nbd)](+) 7(+), [(eta-cod)Rh{mu-B(pz)(4)}Ir(eta-cod)](+) 8(+) and [(eta-cod)Rh{mu-B(pz)(4)}Rh(CO)(2)](+) 9(+) produced a mixture of [L(2)M{mu-B(pz)(4)}ML(2)](+), [L'(2)M'{mu-B(pz)(4)}M'L'(2)](+) and the desired species. The heterobimetallic complexes [L(2)Rh{mu-B(pz)(4)}M'Cl(2)] (M' = Co, L(2) = eta-cod 10; M' = Co, L(2) = eta-nbd 11; M' = Co, L = CO 12; M' = Co, L(2) = (CO)(PPh(3)) 13; M' = Zn, L(2) = eta-cod 14; M' = Zn, L(2) = eta-nbd 15; M' = Pd, L(2) = eta-cod 16) possess square planar Rh(I) linked to square planar Pd(II) or tetrahedral Zn(II) and Co(II) centres. The paramagnetic Co(II) complexes give (1)H NMR spectra with signals shifted over a range of 75 ppm. The UV-Vis spectra of 10-13 show four bands, one MLCT at Rh and three d-d transitions arising from the splitting of the (4)T(1)(P) excited state due to approximate C(2v) symmetry at Co.