Synthesis and Characterization of Dimethylbis(2-pyridyl)borate Nickel(II) Complexes: Unimolecular Square-Planar to Square-Planar Rotation around Nickel(II) | Zendy

Jeff Joseph A. Celaje | Zendy; Megan K. PenningtonBoggio | Zendy; Robinson W. Flaig | Zendy; Michael G. Richmond | Zendy; Travis J. Williams | Zendy

Open Access

Synthesis and Characterization of Dimethylbis(2-pyridyl)borate Nickel(II) Complexes: Unimolecular Square-Planar to Square-Planar Rotation around Nickel(II)

Author(s) -

Jeff Joseph A. Celaje,

Megan K. PenningtonBoggio,

Robinson W. Flaig,

Michael G. Richmond,

Travis J. Williams

Publication year - 2014

Publication title -

organometallics

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.231

H-Index - 172

eISSN - 1520-6041

pISSN - 0276-7333

DOI - 10.1021/om500173j

Subject(s) - chemistry , nickel , planar , activation energy , crystallography , boron , ring flip , dichloromethane , solvent , ring (chemistry) , organic chemistry , computer graphics (images) , computer science

The syntheses of novel dimethylbis(2-pyridyl)borate nickel(II) complexes 4 and 6 are reported. These complexes were unambiguously characterized by X-ray analysis. In dichloromethane solvent, complex 4 undergoes a unique square-planar to square-planar rotation around the nickel(II) center, for which activation parameters of Δ H ⧧ = 12.2(1) kcal mol -1 and Δ S ⧧ = 0.8(5) eu were measured via NMR inversion recovery experiments. Complex 4 was also observed to isomerize via a relatively slow ring flip: Δ H ⧧ = 15.0(2) kcal mol -1 ; and Δ S ⧧ = -4.2(7) eu. DFT studies support the experimentally measured rotation activation energy (cf. calculated Δ H ⧧ = 11.1 kcal mol -1 ) as well as the presence of a high-energy triplet intermediate (Δ H = 8.8 kcal mol -1 ).

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