{Supplementary Data}

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Crystal structure data

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NMR spectra of cis-Pd(MeN₃OC₆H₄Me-2)₂ in CDCl₃ at different temperatures. The signals for 2-Me groups at high-field are omitted

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Temperature dependence of NMR spectra of cis-Pd(MeN₃OC₆H₄Bu^t-2)₂ in d₈-toluene

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Temperature dependence of NMR spectra of cis-Pd(PrⁱN₃OC₆H₄Bu^t-2)₂ in d₈-toluene

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Temperature dependence of NMR spectra of cis-Pd(MeN₃OC₆H₃Me-2,4)₂ in d₈-toluene

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NMR spectra of cis-Pd(PrⁱN₃OC₆H₃Me-2,4)(MeN₃OC₆H₄Cl-4) and cis-Pd(MeN₃OC₆H₃Me-2,6)₂ in d₈-toluene

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NMR spectra of cis-isomers of Pd(OMeN₃C₆H₃Me-2,4)(OPrⁱN₃C₆H₃Bu^t-2), Pd(OMeN₃C₆H₃Me-2,4)(OPrⁱN₃C₆H₄Cl-4), Pd(OMeN₃C₆H₃Me-2,4)(OPrⁱN₃C₆H₃Me-2,6), Pd(OMeN₃C₆H₃Me-2,4)(OEtN₃C₆H₃Me-2,6) and Pd(MeN₃OC₆H₃Me-2,4)₂ at room temperature in d₈-toluene

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NMR spectrum of cis-Pd(OMeN₃C₆H₃Me-2,5)(OMeN₃C₆H₃Bu^t-2)

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2D NOESY spectra of cis-Pd(OMeN₃C₆H₃Me-2,5)(OMeN₃C₆H₃Bu^t-2). Different peaks are shown in Charts A, B and C:

Chart A

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Chart B

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Chart C

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Temperature dependence of the NMR spectra of cis-Pd(OMeN₃C₆H₃Me-2,4)(OPrⁱN3C₆H₃Bu^t-2) in d₈-toluene. Only the aliphatic region is shown

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Aliphatic region of the NMR spectrum of trans-Pd(OMeN₃C₆H₃Me-2,Et-6)₂ at different temperatures

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NMR spectrum of trans-Pd(PrⁱN₃OC₆H₄Bu^t-2)₂ in d₈-toluene at 273 and 191 K

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COSY spectra of cis-Pd(MeN₃OC₆H₄Bu^t-2)₂ in d₈-toluene

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NOESY spectra of cis-Pd(MeN₃OC₆H₄Bu^t-2)₂ in d₈-toluene

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COSY spectra of cis-Pd(MeN₃OC₆H₃Me-2,5)₂ in d₈-toluene

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NOESY spectra of cis-Pd(MeN₃OC₆H₃Me-2,5)₂ in d₈-toluene

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NOESY spectrum of cis-Pd(OMeN₃C₆H₄Bu^t-2)(OPrⁱN₃C₆H₃Me-2,6)

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