Immobilization of palladium­(II) acyclic diaminocarbene (Pd­(II)-ADC) complexes on a resin support surface has been easily performed by metal-mediated addition of amino groups of benzhydrylamine-polystyrene to the coordinated isocyanide ligand of cis-PdCl2(CNR)2 (R = t-Bu, Cy). The investigation of the benzhydrylamine reaction with palladium-coordinated isocyanides in solution has revealed that, depending on the reaction conditions, two carbene-type complexes can be obtained as a result of the addition to the CN triple bond, as well as a third complex which is formed via substitution of the isocyanide ligand by benzhydrylamine. Nucleophilic addition of an amino group to the isocyanide ligand has led to a cis-acyclic diaminocarbene complex or a cationic diaminocarbene complex with trans configuration and an intramolecular hydrogen-bonded chloride anion (the nature of this noncovalent interaction was analyzed by DFT calculations, including AIM analysis). The unsupported and resin-supported palladium catalysts have demonstrated high catalytic activity in both Sonogashira and Suzuki–Miyaura cross-coupling. The supported catalyst can be recovered and repeatedly reused without a significant loss in efficiency. The degree of the palladium binding with polystyrene, the oxidation state, and the palladium leaching level were investigated by XPS and XRF analyses.

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Well-defined diazotates are scarce. Here we report the synthesis of unprecedented homoleptic palladium(II) diazotate complexes. The palladium(II)-mediated nitrosylation of 2-aminopyridines with NaNO results in the formation of metal-stabilized diazotates, which were found to be cytotoxic to human ovarian cancer cells.

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Two types of immobilized on the amino-functionalized polystyrene-supported acyclic diaminocarbene palladium complexes (ADC-Pd II ) are investigated under Sonogashira cross-coupling conditions. Depending on substituents in the diaminocarbene fragment immobilized ADC-Pd II , systems are found to have different catalytic activity and stability regarding Pd-leaching. Pd II -diaminocarbenes possessing protons at both nitrogen atoms smoothly decompose into Pd 0 -containing species providing a catalytic "cocktail system" with high activity and ability to reuse within nine runs. Polymer-supported palladium (II) complex bearing NBn-C carbene -NH-moiety exhibits greater stability while noticeably lower activity under Sonogashira cross-coupling. Four molecular ADC-Pd II complexes are also synthesized and investigated with the aim of confirming proposed base-promoted pathway of ADC-Pd II conversion through carbodiimide into an active Pd 0 forms.

A new convenient approach to the synthesis of useful N-heterocyclic carbene complexes of group 13 metals was successfully developed. We demonstrate that air-stable copper(I) diaminocarbene complexes are excellent carbene transfer...

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