Abstract
The synthesis and structure is reported of TpPh,4CNNi(NO3)(EtOH) or [Ni(C30H19BN9)(NO3)(C2H6O)], the first half-sandwich complex of a cyano-scorpionate ligand. The pseudo-octa-hedral coordination sphere of the NiII ion is comprised of a tridentate tris-(4-cyano-3-phenyl-pyrazol-yl)borate ligand, a bidentate nitrate ligand and a neutral ethanol ligand. The phenyl substituents on the TpPh,4CN ligand are relatively parallel to the planes of the ethanol and nitrate ligands. An inter-molecular hydrogen-bonding inter-action is evident between the ethanol OH group and the pyrazole CN substituent. The ethanol ligand was modeled with a 0.572 (13)/0.428 (13) disorder of the methyl C atom.
Highlights
The synthesis and structure is reported of TpPh,4CNNi(NO3)(EtOH) or [Ni(C30H19BN9)(NO3)(C2H6O)], the first half-sandwich complex of a cyanoscorpionate ligand
The pseudooctahedral coordination sphere of the NiII ion is comprised of a tridentate tris(4-cyano-3-phenylpyrazolyl)borate ligand, a bidentate nitrate ligand and a neutral ethanol ligand
The phenyl substituents on the TpPh,4CN ligand are relatively parallel to the planes of the ethanol and nitrate ligands
Summary
Scorpionate, or trispyrazolylborate (Tp), ligands were shown early in their existence to readily form octahedral sandwich complexes (Tp2M) with transition metals (Trofimenko, 1966; Trofimenko, 1967). Trofimenko and coworkers reported, in 1987, the synthesis of TpPh, which they showed was resistant to formation of such complexes due to the bulk of the phenyl substituents (Trofimenko et al, 1987). Eichhorn and Armstrong showed that this ligand could still form sandwich compounds with increased M—N bond lengths (Eichhorn & Armstrong, 1990). The Ni—N bond lengths [2.079 (2)–2.103 (2) A ; Table 1] are similar to those in TpPh,4CNBpPh,4CNNi
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