An iridium pincer complex has been immobilised in the metal–organic framework NU-1000. The stable Ir-pincer modified NU-1000 is catalytically active in the hydrogenation of alkenes in condensed phase and under flow conditions.

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The electronic effects of bulky aryl substituents on low coordinated phosphorus atom(s) in diphosphenes and phosphaalkenes have been examined by means of functionalization at the para position of the substituents. Bulky bromobenzenes bearing an electron-donating or electron-withdrawing group at the para position were prepared as precursors of the substituents and some of them were applied to preparations of the corresponding diphosphenes and fluorenylidene(phenyl)phosphines bearing low-coordinated phosphorus atom(s). Electronic perturbation by the para-substituent in the system was indicated by UV–vis spectra and 31P NMR chemical shifts. These observations can be attributed to effects induced by electronic properties of the bulky aryl substituent(s) on the lone pair of the low-coordinated phosphorus atom.

Compounds with two ferrocenyl units connected with 3,4-diphosphinidenecyclobutene (DPCB) linkers at the 1,2-positions (1) and their transition metal chelate complexes (2) were prepared, and the spectroscopic and electrochemical properties were studied. The compounds were examined by cyclic voltammetry, and ∆E 1/2 values (the separation between successive Fe 2+ /Fe 3+ oxidation potentials) were determined. Being fully conjugated with DPCB linkers, those compounds demonstrated electrochemical communication: the Cr(CO) 4 complex of 1 (2Cr) showed a strong interaction (∆E 1/2 ) 350 mV), whereas PdCl 2 and PtCl 2 complexes of 1 (2Pd and 2Pt) displayed a decreased interaction compared to that of 1.

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Sterically protected 1,2-bis[(2,4,6-tri-t-butylphenyl)phosphinidene]cyclobuta[l]phenanthrene (4) and its group(6) and group(10) transition metal complexes were prepared. X-ray crystallographic analysis of 4 revealed a planar structure of the diphosphinidenecyclobuta[l]phenanthrene moiety.

A new bulky bromobenzene, 2-bromo-1,3-di-tert-butyl-5-methoxybenzene, was prepared and utilized to preparations of the corresponding diphosphene and fluorenylidenephosphine including low-coordinate phosphorus atom(s). An electronic perturbation of the p-methoxy group in the system was indicated by UV–vis spectra and 31P NMR chemical shifts.

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