Abstract
Addition of H2 to the precursor [Rh(Cyp2PCH2CH2PCyp2)(η2:η2-C7H8)][BArF4] gives the σ-alkane complex [Rh(Cyp2PCH2CH2PCyp2)(η2:η2-C7H12)][BArF4] by a single-crystal to single-crystal reaction, as characterized by X-ray crystallography, SSNMR spectroscopy, and periodic DFT. An unexpected rearrangement of the {Rh(L2)}+ fragment is revealed.
Highlights
[BArF4]R = Cy, the σ-alkane complex is stable in the solid state for months at 298 K.5
We report the synthesis of [Rh(Cyp2PCH2CH2PCyp2)(η2:η2-NBA)][BArF4] using a cyclopentyl (Cyp)-substituted chelating phosphine[6] which was designed to sit between the steric profiles of flexible iBu and rigid/tall Cy
The [BArF4]− anions are organized so that each cation is contained within a pseudooctahedral cage of anions, and the overall motif and structural
Summary
Both species feature encapsulation of the cation by an octahedral arrangement of [BArF4]− anions, which provides a well−defined lattice environment, while the buttressing Cy groups in [2-NBA][BArF4] may install a kinetic penalty toward rearrangement in the solid state.[4,5] We report the synthesis of [Rh(Cyp2PCH2CH2PCyp2)(η2:η2-NBA)][BArF4] using a cyclopentyl (Cyp)-substituted chelating phosphine[6] which was designed to sit between the steric profiles of flexible iBu and rigid/tall Cy. This leads to a relatively stable σ-alkane complex and an unexpected metal-fragment reorientation within the [BArF4]− anion cavity while retaining the integrity of the single crystal.
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