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Issue 12, 2008
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Structure–solid-state CPMAS 13C NMR correlation in palladacycle solvates (pseudo-polymorphs) with a transformation from Z′ = 1 to Z′ = 2

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Abstract

The dinuclear µ-acetato-µ-benzophenone iminato palladium complex [{(CN)Pd}2(µ-OAc)(µ-N[double bond, length as m-dash]CPh2)] (1) [CN = N,N-dimethylbenzylamine-κNC)] is prepared by reaction of [{(CN)Pd(µ-OAc)}2] with benzophenone imine and [NBu4]OH in ethanol. The dinuclear palladacycle 1 can crystallize with different solvents molecules as 1·1.5C6H5CH3, 1·0.25C6H5CH3 (Z′ = 2), 1·1.5C6H6 and 1·C6H14 (n-hexane) upon hexane diffusion into a toluene, benzene or CH2Cl2 solution, respectively. The structure of 1·0.25C6H5CH3 with two palladacycle molecules and two partly occupied toluene molecules in the asymmetric unit (Z′ = 2) is a consequence of partial toluene solvent loss from 1·1.5C6H5CH3 (Z′ = 1) as was followed by solid-state CPMAS 13C NMR. The transformation from Z′ = 1 to Z′ = 2 (crystal “on the way”?) toluene solvate can proceed in a solid-state single-crystal-to-crystal transition as evidenced from multiple single-crystal X-ray diffraction studies, also when the crystals are still in their mother liquor. During this transformation the remaining toluene crystal solvent becomes “locked in” (immobile from static 2H (D) NMR, only lost above 80° from TGA) and the crystals of 1·0.25C6H5CH3 (Z′ = 2) remain crystalline in air in the absence of mother liquor or toluene, different from the other solvates. A rotational disorder of one of the benzene molecules in 1·1.5C6H6 (Z′ = 1) around its pseudo-six-fold axis is supported by the line-shape analysis of the static 2H (D) spectrum.

Graphical abstract: Structure–solid-state CPMAS 13C NMR correlation in palladacycle solvates (pseudo-polymorphs) with a transformation from Z′ = 1 to Z′ = 2

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Publication details

The article was received on 14 Jul 2008, accepted on 02 Oct 2008 and first published on 23 Oct 2008


Article type: Paper
DOI: 10.1039/B812012A
Citation: CrystEngComm, 2008,10, 1928-1938
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    Structure–solid-state CPMAS 13C NMR correlation in palladacycle solvates (pseudo-polymorphs) with a transformation from Z′ = 1 to Z′ = 2

    J. Ruiz, V. Rodríguez, N. Cutillas, A. Hoffmann, A. Chamayou, K. Kazmierczak and C. Janiak, CrystEngComm, 2008, 10, 1928
    DOI: 10.1039/B812012A

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