Pyrazolate Coordination Continues To Amaze���The New��-��²:��¹Binding Mode and the First Case of Unidentate Coordination to a Rare Earth Metal

Anion-tuning of supramolecular gel properties

“…54,61,77,78,88,93,98,[123][124][125][126][127][128][129][130][131][132][133][134][135] There have been some classical host:guest systems developed that can be used as LWMGs. An interesting host:guest system of cucurbit [7]uril (1.8) in acidic water was shown by Kim et al 1.8 to only gel in aqueous solutions at pH values below its pK a , which was determined to be 2.2 by a simple titration method.…”

“…[1][2][3][4][5]8,18,[111][112][113][114][115][116][117][118] Prior to 1997, the coordination modes established for pyrazolate by crystallographic means consisted of just the simple μ-η The synthesis of homoleptic pyrazolate complexes of both d-block, f-block and main group metals has also been achieved. 119,123,124 In all these cases, there is significant competition between the formation of the homoleptic complex and complexes with coordinated solvent. 3,5-Di-tbutylpyrazole (TBPH) is an archetypal ligand when it comes to the coordination chemistry of the pyrazolates.…”

“…112,124,125 Due to its simplicity in structure and its lack of steric bulk it forms many types of complex with all known metal types. 119,123,124 The homoleptic [Al(TBP) 3 ] has been synthesised (Compound 3.12, a hexane solvate trigonal crystal structure was determined) using a metathesis method.…”

Synthesis and structural characterization of (CH2)n-bridged indenyl-pyrazoles and their cyclopentadienyl nickel(II) complexes

“…Pyrazolato ligands have demonstrated rich coordination chemistry due to their diverse coordination modes to metals [1][2][3][4][5][6][7][8][9][10][11]. Pyrazoles and pyrazolato ligands are potentially useful in design of transition metal complex catalysts [12] and construction of metal architectures [13].…”

“…Pyrazoles have exhibited versatile reactivity to organometallic compounds, forming a wide range of pyrazolato complexes [1][2][3][4][5][6][7][8][9][10][11][12]. The reactions of nickelocene with 4-X-3,5-dimethylpyrazole (X = H, Cl, Br, CH 3 , and NO 2 ) and 3,5-bis(perfluoromethylpyrazole) in benzene were reported to form dimetallic (at room temperature) and trimetallic (at elevated temperature) cyclopentadienyl nickel(II) pyrazolato complexes, i.e., [CpNi(4-X-3,5-RR 0 Pz) 2 ] 2 Ni and [CpNi(4-X-3,5-RR 0 Pz)] 2 [28].…”