Pyridylborates as a New Type of Robust Scorpionate Ligand: From Metal Complexes to Polymeric Materials

Abstract

The importance of scorpionate ligands in modern coordination chemistry continues to increase, because of their outstanding versatility, tunability and user-friendliness. Herein, we provide a short overview of recent developments in the classes of scorpionate ligands, derived from pyrazoles, triazoles, imidazoles, oxazolines, thioimidazoles and other similar systems, followed by an in-depth discussion of a new type of ro- Classes of Scorpionate LigandsScorpionate ligands [1] are facially coordinating tridentate chelates, which have evolved into one of the most useful and [a]

Coordinating Tectons. Experimental and Computational Infrared Data as Tools To Identify Conformational Isomers and Explore Electronic Structures of 4-Ethynyl-2,2′-bipyridine Complexes

“…Half-sandwich ruthenium phosphino σ-alkynyl complexes Ru(C≡CR)L 2 Cp' (L = phosphine-based ligand, Cp' = η 5 81 Alternatively, a desilylation / metallation reaction sequence from RuClL 2 Cp' with Me 3 SiC≡CR in the presence of KF has also been found to be effective in a number of cases. 82 In the present study the terminal alkyne HC C-4-bpy (1) was obtained by desilylation of the analogous trimethylsilyl-protected compound Me 3 SiC≡C-4-bpy (2), which was in turn prepared by Sonogashirabased cross-coupling of 4-bromo-2,2'-bipyridine with trimethylsilylacetylene.…”

“…Complex [8]OTf crystallized with three CHCl 3 solvate molecules, two of the solvent molecules were modelled as being disordered over two sites with occupancies refined to 0.688 (8) and its complement for both molecules. Complex 10 crystallized with two crystallographically distinct molecules in the unit cell, molecule 1 has the bipyridyl moiety disordered over two sites with equal occupancies, molecule 2 has the Cp* ligand disordered over two sets of sites with occupancies refined to 0.712 (5) and its complement, see Figure S-5.…”

“…[1][2][3][4] Metal complexes are now finding application in targeted materials as a consequence of this capacity to fine tune the properties of the metal-ligand assembly. Some of these approaches incorporate ligand architectures into polymers, 5 provide dynamically porous materials, 6 guide the construction of surface based catalysts, 7 and modulate the properties of nonlinear optical materials. 8,9 Robust, and ideally modular, synthetic methodologies that permit ready assembly of metal-containing compounds and complexes would allow facile exploration of the chemical, physical and optoelectronic features provided by metal complexes and design of new materials.…”

The hydridotris(3-nitro-1,2,4-triazol-1-yl)borate, a new nitro-substituted electron withdrawing polydentate “scorpionate”-type ligand and related copper and silver phosphane complexes

“…In the last 50 years the success of poly(pyrazolyl)borates has inspired the development of new scorpionate ligands that are excellent mono-anionic supporting ligands for most metals of the Periodic Table including d-and f-block elements [2][3][4][5][6]. One reason for this success is arising out of their donor versatility by varying the substituents on the boron center, featuring boron-centered scorpionate ligands based on moieties such as thioimidazolyl [7][8][9], selenoimidazolyl [10], phosphane [11][12][13][14][15] and Nheterocyclic carbenes [16][17][18], such as the ease of modifying the steric and electronic environment about the metal center by variation of the azolyl moiety or the substituents on the azolyl groups [3,4,[19][20][21][22][23][24][25][26][27][28].…”

Scorpionate complexes of aza-18-crown-6 containing fluoronitrophenyl substituents as studied by electrospray ionization mass spectrometry

“…Scorpionate complexes are some of the most interesting and recently widely studied . Although scorpionate ligands are usually tridentate, the term ‘scorpionate’ has been also used for cyclams containing nitrophenyl or nitrobenzyl substituents.…”