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- W2036054844 abstract "Examples of symbiotic and antisymbiotic behavior involving ambidentate ligands such as the NCS− ion have thus far been restricted to, respectively, octahedral complexes of class ‘a’ metals and square planar complexes of class ‘b’ metals. In the latter case, only the strong trans-influence of π-acid ligands heretofore been observed to cause antisymbiosis. The title complex was chosen for study because it involves an octahedral complex of an ambidentate ligand and class ‘b’ metal (re: [lr(SCN)6]3−) wherein the former is subjected to the strong trans-influence of a ligand which can only function as a σ-base. In the solid state, antisymbiosis is demostrated by the stability of the N-bound trans-[lr(pip)4H(NCS)]NCS, and counteranion control by the synthesis and stability of the S-bound isomer as the BPh4− salt. When trans-[lr(pip)4(NCS)(H)]NCS or its BPh4− salt as put into solution, IR studies indicate that N-bonding initially prevails in solution, irrespective of solvent dielectric. The prolonged aging of methylene chloride solutions of either trans-[lr(pip)4(NCS)(H)]NCS or of trans-(pip)4(SCN)(H)BPh4 produces the soluble cation trans-[lr(pip)4(SCN)2]+. The νCN frequency of the noncoordinated NCS− is remarkably sensitive to the solvent dielectric, suggesting the existence of H-bonding to the amine proton of the piperidine ligands in the low dielectric solvents. NMR data support the existence of the mixture of six- and seven-coordinate species in all solvents forthe NCS− salt, as a consequence of the observation for each solution of a doublet hydride resonance. Solutions of the BPh4− salt, on the other hand, exhibit only a single hydride resonance, indicating the presence of the only a six-coordinate moiety." @default.
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- W2036054844 date "1976-01-01" @default.
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- W2036054844 title "Symbiosis versus antisymbiosis: a study of the thiocynate bonding mode in trans-hydridothiocyanatotetrakispiperidineiridium(III) thiocyanate and tetraphenylborate" @default.
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- W2036054844 doi "https://doi.org/10.1016/s0020-1693(00)95585-3" @default.
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