European Journal of Inorganic Chemistry

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The files contain the Nuclear Magnetic Resonance spectra of all compounds reported within this publication. All NMR files are processed MestReNova files, which are easily interpretable and can be used for facile comparison with locally produced spectra. Raw FIDs can readily be extracted with the same software.

This dataset contains X-band CW-EPR spectra of a Co(II)-salen type complex recorded at various temperatures and in the presence of various coordinating substrates. EPR relaxation measurements are also included. The simulated EPR spectra are also included. DFT energy optimised output files (.log) are presented along with orbital output files (.fchk). DFT computed Spin Hamiltonian calculation details are also incorporated (.prop). The data reveals how the spin states of the molecular complex can be altered depending on the coordinating substrate.

Supplementary information files for article Dinuclear Palladium(II) and Platinum(II) Complexes of a Readily Accessible Bicyclic Diphosphane The one-step synthesis (33 % isolated yield) of a novel bicyclic diphosphane, [P(CH2)2NC6H4(4-NMe2)]2, P−P(NMe2), from the reaction of [P(CH2OH)4]Cl and H2NC6H4(4-NMe2) in methanol is described. Surprisingly, P−P(NMe2) displays excellent air/solution stability (towards H2O, CH3OH) and can also function efficiently as a bridging ligand. Hence reaction of P−P(NMe2) with [Pd(μ−Cl)(η3-allyl)]2 (η3-allyl=C3H5, C4H7) or [Pd(μ−Cl)(κ2−C9H12N)]2 affords the singly-bridged complexes {Pd(Cl)(η3-allyl)}2 {μ-P−P(NMe2)} 1 a/1 b and {Pd(Cl)(κ2−C9H12N)}2{μ-P−P(NMe2)} 1 c whereas treatment with [MX2(η4-cod)] (M=Pd, Pt; X=Cl, Br, I, Me; η gave the corresponding dimethylammonium salts 3 a–d. Single crystal X-ray studies have been undertaken on P−P(N4-cod=cycloocta-1,5-diene) gave (MX2)2{μ-P−P(NMe2)}2 2a–e in high yields. Protonation of 2 a–d with HBF4 ⋅ OEt2Me2), 1 b, 2 a, 2 b ⋅ 2CDCl32, 2 d, 2 e, 3 a ⋅ 12CD3CN and 3 b ⋅ 12CD3CN. The P−P bond lengths in free/coordinated P−P(NMe2) remain similar across all compounds studied here and no M ⋅⋅⋅ M contacts were observed within the planar M2P4 ring. In 3 a/3 b the BF4− anion displays a unique secondary interaction with the inorganic six-membered M2P4 core.

The hydrolysis of UO22+, NdIII , CeIII and CeIV cations, induced by thermal decomposition of urea, was studied. Moreover, we investigated binary mixtures of uranyl and the lanthanides, as well as ternary mixtures of uranyl and both lanthanides using CeIII or CeIV. The impact of the urea content and the temperature on the reaction kinetics and the formed precipitate was evaluated and the results are in depth discussed in our article, some results are also summarised in this presentation. Uranyl ions precipitated as ammonium diuranate (ADU) with different stoichiometry under the applied conditions. NdIII and CeIII cations showed a comparable pH evolution during hydrolysis and LnCO3OH products were identified, whereas CeIV hydrolysed at a lower pH and formed nanocrystalline CeO2. Depending on the urea content, a partial co-precipitation was observed for mixtures of UO22+ and NdIII. The products of CeIII and CeIV hydrolysis were also identified in the precipitates of binary uranyl and cerium mixtures. For ternary U/Nd/Ce mixtures, a simultaneous precipitation of NdIII and CeIII and a partial incorporation of the Ln phase into the ADU phase was observed, whereas the presence of CeIV/CeO2 resulted in three individual phases. The precipitation reaction was followed by monitoring the pH evolution and the metal concentration in the supernatant, applying UV/Vis and ICP-MS. The formed precipitates were characterised by XRD and SEM. The data accrued during the study are part of this data set. Please note that the provision of this dataset is based on a voluntary basis. You are welcome to use the data from this set in your work. If you do so and publish resulting findings, please cite our work as required by the license.

Supplementary Information files for Synthesis and characterisation of transition metal complexes of a novel 1,5‐benzodiazepine‐functionalised tertiary phosphine The one-step synthesis (44% isolated yield) of the 1,5- benzodiazapine functionalised phosphine 1, C31H31N2OP, is reported. Bridge cleavage of {MCl(μ-Cl)(η5 -Cp*)}2 (M=Ir, Rh) with 2 equiv. of 1 in CH2Cl2 gave the mononuclear compounds [MCl2(η5 -Cp*)(P-1)] (M=Ir, 2a; M=Rh, 2b) in which 1 functions as a P-monodentate ligand. Rapid C(sp3 ) H bond activation, at room temperature, is observed for 2a leading to the unusual cyclometallated complex [Ir(η5 -Cp*)(P,N,C-1)]Cl2 3 (or 3‘) bearing an anionic P/Namine/C-terdentate ligand. Reaction of [Pt(CH3) Cl(η4 -cod)] with one equiv. of 1 led to [Pt(CH3)Cl(P,N-1)] 4, suggesting that 3 may form via an intermediate IrIII cationic species in which the ligand is P,N-bound. The IrI complex [IrCl (η4 -cod)(P-1)] 5 does not, under similar conditions, show any evidence for C H activation. Single crystal X-ray studies on 1, 2a, 2b, 3, 3‘, 4, and 5 reveal intramolecular N···H O H-bonding in all cases.

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