Tris borate chemistry

The phase relations, stoichiometry and structural chemistry of the metal borates have been extensively studied because of their geochemical implications and technological importance. Borates are known in which the structural unit is mononuclear (1 B atom), bi-, tri-, tetra- or penta-nuclear, or in which there are polydimensional networks including glasses. The main structural principles underlying the bonding in crystalline metal borates are as follows " ... 

The family of poly(pyrazol-l-yl)borates has been widely used as supporting ligands in nickel coordination chemistry.556,557 Complex (191) is an example, where unusual cysteine coordination is achieved at a tris(pyrazolylborate)nickel(II) template.601 (191) undergoes rapid reaction with molecular oxygen to presumably form a sulfinate. 

During the course of modeling copper dioxygen chemistry, Kitajima et al. reported the synthesis of a yu-peroxo dinuclear complex with a 3,5-dimethyl-substituted tris(pyrazolyl)borate ligand, which showed remarkable physicochemical similarities to oxy-Hc and oxy-Tyr. Using a 3,5-di-isopropyl-substituted terminal ligand, they provided the first structural proof of the existence of peroxo dicopper(II) core (108) (copper geometry distorted square pyrami-... 

Hydride reductions of C = N groups are well known in organic chemistry. It was therefore obvious to try to use chiral auxiliaries in order to render the reducing agent enantioselective [88]. The chiral catalyst is prepared by addition of a chiral diol or amino alcohol, and the active species is formed by reaction of OH or NH groups of the chiral auxiliary with the metal hydride. A major drawback of most hydride reduction methods is the fact that stoichiometric or higher amounts of chiral material are needed and that the hydrolyzed borates and aluminates must be disposed of, which leads to increased costs for the reduction step. 

The Tp hgands (i.e., tris(pyrazolyl)borates or scorpionates [13]) are close analogs to the Cp hgands (i.e., -cyclopentadienyl), and in connection with the chemistry of the Tp Cr complexes mentioned above, a recent example of O2-binding from vanadium chemistry is of interest, even though it is formally not organometalhc chemistry Reaction of the V(IV) complex... 

NMR (CeDg, 125.7 MHz, 25°C) 139.8, 132.5, 128.8-129.1 (overlapping resonances), 124.6, 17.0 (br). B NMR (CgDg, 128.3 MHz, 25°C) -10.96 ppm. The compound is a versatile precursor to a wide range of transition metal complexes supported by the tris(phosphino)borate ligand. It is air- and water-stable for extended periods, and, unlike the lithium and ammonium salts of [PhB(CH2PPh2)3] , it is both soluble and stable in chloroform and dichloromethane for days, making these useful solvents available for subsequent trans-metallation chemistry. 

The tris(N-(3-tm-butyl)pyrazolyl)methane ligand, with an extremely bulky 3-substituent, favors the formation of tetrahedral complexes2 in much the same way as observed in the chemistry of the hydrotris(3-tert-butyl-pyrazolyl)borate ligand.1... 

A side-on p,-Tq2 Tq2-peroxo dicopper(II) complex. A very important development in copper-dioxygen chemistry occurred in 1989 with the report by Kitajima et al. [10,108] that another Cu202 species could be prepared and structurally characterized by using copper complexes with a substituted anionic tris(pyrazolyl)borate ligand. This intensely purple compound, Cu[HB(3,5-iPr2pz)3] 2(02) (5), was prepared either by reaction of Cu[HB(3,5-iPr2pz)3] (4) with 02 or by careful addition of aqueous hydrogen peroxide to the p-dihydroxo... 

Following their investigations on nitrene, carbene, and oxo transfer reactions catalyzed by fluorinated silver tris(pyrazoyl)borate (see Chapter 6 on nitrene chemistry), Lovely et al. looked for a combined carbene transfer and [2,3]-sigmatropic rearrangement. On the basis of these mechanistic considerations, these authors showed that diazoacetates, indeed, reacted with allyl halides in the presence of this silver catalyst to give a-halo-y-unsaturated esters (Scheme 3.51).77... 

Keywords Bioorganometallic chemistry Medicinal organometallic chemistry Metal carbonyls Metallocenes N-heterocyclic carbenes Peptides Peptide Bioconjugates Peptide synthesis Solid phase synthesis Tris(pyrazolyl)borate ligands... 

Several research groups have studied the chemistry of tris(pyrazolyl)borate tricarbonyl complexes of technetium and rhenium. As depicted in Scheme 28, these studies allowed the synthesis of/ac-[M(CO)3Tp ] [M is Tc, Re, Tp is Tp (111/113), Tp (112/114)] complexes, which were all structurally characterized. Complexes 111-114 were synthesized by reaction of the classical starting materials [M(CO)5Br] with the sodium or potassium salts of the correspondent Tp ligands [121-123]. 

More recently, great attention has been given to the chemistry of M(I) (M is Tc, Re) tricarbonyl complexes with bis(mercaptoimidazolyl)borates and tris(mer-captoimidazolyl)borates, searching for target-specific radiopharmaceuticals based on the/ac-[M(CO)3]+ moieties (M is 99mTc, 186/188Re) [127-129]. 

Studies on the basic coordination chemistry of rhenium and technetium with tris(pyrazolyl)borates demonstrated that water-stable Re(VII) trioxides... 

Substituted tris(pyrazolyl)borates were recently employed as silver(l) ligands due to their ability to yield heat and air stable metal complexes. Two research groups have prepared very similar sUver(l)-tris(pyrazolyl)borate compounds for catalyzing carbene insertion chemistry. Both systems require electron-withdrawing groups on the tris(pyrazolyl)borate ligands to stabilize the sUver(l) complexes and enhance the electrophilicity of the putative silver-carbenoids (129,130). Dias et al. (129) found that, with CF3 substitutes, a complex of [HB(3,5-(Cp3)2pz)3] Ag(thf) could activate ethyl diazoacetate (EDA) to react with different C X (X = Cl, Br, 1) bonds to afford either C—X bond insertion products or 1,1-hydrochlorination products. At the time of this writing, this unique reactivity was reported only with a silver catalyst (Fig. 27). 

---