para‐Bromophenyl[tris(pyrazolyl)]borate Complexes of Group 1 Metals, Thallium and Magnesium: Synthesis and Characterization of Transfer Agents for “Third‐Generation” Tp Ligands

Abstract

In the course of finding ligands suitable for application in bioorganometallic systems, "third-generation" Tp-transfer agents p-BrC 6 H 4 TpM [M = Na (1), K (2), Rb (3), Cs (4), Tl (5)

Advances in alkaline earth-nitrogen chemistry

“…Examples include the monomeric (PhTp tBu )MgR (R = Me, Et; PhTp tBu = phenyl[tris(3-t-butylpyrazolyl)borate]) complexes, displaying approximately tetrahedral geometry, and a magnesium sandwich complex, Mg(p-BrC 6 H 4 Tp) 2 (p-BrC 6 H 4 Tp = parabromophenyl[tris(pyrazolyl)borate]), with a distorted octahedral environment of the magnesium atoms, similar to that reported for the first and second generation MgTp 2 complexes [171].…”

“…Here, we provide only a brief overview of the different ligand types and the main characteristics of the relevant complexes that have not previously been reviewed. Interest in these compounds arises from their applications in atomic layer deposition (ALD) as precursors for electronic materials, and as catalysts and bioorganometallic applications [150,[169][170][171]. As multiple recent reviews are available on the topic, the following discussion will be brief.…”

Synthesis and Characterization of the Azido‐Functionalized Ruthenocene Analogue [TpmRu(p‐N3C6H4)Tp]Cl and Its Attachment to Biomolecules by Copper‐Catalyzed Azide–Alkyne Cycloaddition

“…All reagents and anhydrous solvents were purchased from commercial sources and used as received. [RuH(udmh) 3 4 ], [18] Tpm, [38,39] and TpЈK [10] were prepared according to literature methods. Pentynoic acid-functionalized enkephalin (penty-ENK-OH) was prepared by modification of published procedures on Wang resin (Iris Biotech, Germany), cleaved by treatment with 95 % TFA in DMF, and used after washing with ethyl ether.…”

“…To this end, third-gen- eration derivatives have been developed, which allow functionalization with biomolecules on the boron atom. [9] Recent investigations in our group revealed the functionalized p-bromophenyltris(pyrazolyl)borate (p-BrC 6 H 4 Tp or TpЈ) [10] ligand to be suitable for the preparation of various half and mixed sandwich complexes, [11][12][13] including the ruthenocene analogues Cp iPr RuTpЈ [14] and TpRuTpЈ. [13] Functional conversion of these complexes was achieved by a sequence of lithiation, addition of solid CO 2 , and workup with hydrochloric acid, which provided access to their carboxylic acid-functionalized derivatives.…”

Chemistry of the p-block elements with anionic scorpionate ligands

“…The pentafluorophenyl substituted ligand, however, undergoes a rearrangement such that one of the indazolyl groups has migrated such that it is bonded through the nitrogen in the 2-position, rather than the 1-position ( Figure 15). The related bis(indazolyl)borate is also prepared from the indazole and RTp (R = Ph [83], cymantrene and methylcymantrene [84], 4-BrC6H4 [85]) the ligand is only able to act in a bidentate fashion due to the steric bulk of the group on the bridgehead atom.…”