Runyu Han

Structural and spectroscopic studies on four-, five-, and six-coordinate complexes of zinc, copper, nickel, and cobalt: Structural models for the bicarbonate intermediate of the carbonic anhydrase catalytic cycle

The molecular structures and electronic spectra of a series of four-, five-, and six-coordinate complexes of cobalt, nickel, copper, and zinc, stabilized by tris(pyrazolyl)hydroborato ligands, have been determined. The structural variations that are observed for the series of nitrate and carbonate complexes reveal that the preference for bidentate coordination of these ligands increases across the series Zn < Co ⪡ Cu and Ni.

The tris[3-(9-anthryl)pyrazol-1-yl]hydroborato ligand, [TpAnt]: Compositional disorder between a vacancy and a chain of three atoms

Abstract A new tris(pyrazolyl)hydroborato ligand with anthryl susbtituents in the 3-position, tris[3-(9-anthryl)pyrazol-1-yl]hydroborate, [Tp Ant ], has been synthesized by the reaction of KBH 4 with 3-(9-anthryl)pyrazole and characterized as the thallium derivative, Tl[Tp Ant ]. The thallium reagent was used to prepare the cobalt and molybdenum derivatives, [Tp Ant ]CoNCS and [Tp Ant ]Mo(CO) 2 ( η 3 -CH 2 C(Me)CH 2 ). The molecular structure of [Tp Ant ]CoNCS, contaminated with ca 6% Tl[Tp Ant ], has been determined by X-ray diffraction, thereby providing an example of compositional disorder between a vacancy and a chain of three atoms.

Ligand redistribution reactions of tris(3,5-dimethylpyrazolyl)hydroboratomagnesium alkyl derivatives: crystal structure of {η3-HB(3,5-Me2pz)3}2Mg

Abstract Tris(pyrazolyl)hydroboratomagnesium alkyl derivatives {η 3 -HB(3,5-Me 2 pz) 3 }-MgR (3,5-Me 2 pz = 3,5-C 3 N 2 Me 2 H; R = CH 3 , CH 2 CH 3 , (CH 2 ) 3 CH 3 , CH(CH 3 ) 2 , C(CH 3 ) 3 , CHCH 2 , C 6 H 5 ) undergo ligand redistribution reactions, analogous to the Schlenk equilibrium, to give the bis complex {η 3 -HB(3,5-Me 2 pz) 3 } 2 Mg. In contrast, magnesium alkyl derivatives of the more sterically demanding tris(3-t-butylpyrazolyl)hydroborato ligand, {η 3 -HB(3-Bu t pz) 3 }MgR (3-Bu t pz = 3-C 3 N 2 Bu t H 2 ), are stable with respect to the formation of {η 3 -HB(3-Bu t pz) 3 } 2 Mg.

Competitive alkyl and halide metathesis in the reactions of grignard reagents with Tl{η3-HB(3-Butpz)3}

Abstract The reactions of Grignard reagents RMgX [RMgX = CH3MgCl, CH3MgBr, CH3MgI, CH3CH2MgCl, (CH3)2CHMgCl and (CH3)3CMgCl] with Tl{η3-HB(3-Butpz)3} (3-Butpz = 3-C3N2ButH2) show that metathesis of the MgR bond is favoured for X = Cl, Br, whereas metathesis of the MgX bond is favoured for X = I.

Reaction of O2 with {η3-HB(3-Butpz)3}MgCH2Si(CH3)3: Facile SiC bond cleavage and formation of {η3-HB(

Abstract The reaction of the magnesium trimethylsilylmethyl complex {η3-HB(3-Butpz)3}MgCH2Si(CH3)3 with O2 gives the trimethyl

Tris(3-tert-butylpyrazolyl)hydroborato zinc hydride: synthesis, structure and reactivity of a monomeric zinc hydride derivative

The monomeric zinc hydride derivative {η3-HB(3-Butpz)3}ZnH has been synthesized by the reaction of ZnH2 with Tl{η3-HB(3-Butpz)3} and its reactivity investigated.