Molecular dinitrogen complexes of ruthenium(II) porphyrins

A Facile Route to Carbonylhalogenometal Complexes (M = Rh, Ir, Ru, Pt) by Dimethylformamide Decarbonylation

“…Carbon monoxide and dimethylamine have also been found as the sole products of the decomposition of DMF photocatalyzed by a ruthenium compound containing a porphyrin ligand. [37] In the course of our investigations on noble metal catalyzed carbonylation reactions, we have undertaken a comprehensive study of the reactions of RhCl 3 ·3H 2 O, IrCl 3 ·3H 2 O, RuCl 3 ·3H 2 O, K 2 PtCl 4 , PdCl 2 , and Na 2 PdCl 6 with DMF and other amides. Preliminary results of our investigations of the reactions of RhCl 3 ·3H 2 O and IrCl 3 ·3H 2 O with DMF have already been reported.…”

Routes to dicationic ruthenium(II) nitrile complexes containing chelating diphosphine ligands: X-ray analyses of Ru(dppb)(MeCN)42+ 2PF6−(dppb = Ph2P(CH2)4PPh2) and trans-RuCl2(MeCN)4

“…Even the shorter Ru-N bonds, however, are slightly longer than -2.0 A, the sum of the estimated single covalent radii (17), implying little Ru(II)+N, d~-~T T backbonding. Where such backbonding is significant, shorter Ru-N bonds are observed, as, for example, in Ru(I1)-N, complexes: although the accuracy of crystallographic data for dinitrogen complexes is sometimes low, the more reliable Ru-N bond lengths of 1.822 (13) A (18) and 1.894 (9) A (19) in Ru-porphyrin and -bis(ethylenediamine) species, respectively, are significantly shorter than those in the Ru(I1)-nitriles. The C-N bond lengths in the four nitrile complexes range from 1.12 to 1.14 A, being slightly shorter than the value of 1.157 A calculated for MeCN in the gas phase (20), as commonly observed in both transition metal (21) and main group (22) complexes of nitriles.…”

Alkyne and alkene complexes of (tetramesitylporphyrinato)ruthenium(II)

“…In the present work, the reactions of the Ru(TMP) complex (14,15) with acetylene, phenylacetylene, diphenylacetylene, ethylene, and cyclohexene are studied, and organometallic products are prepared and characterized.…”

“…Bis-dinitrogen(tetramesitylporphyrinato)ruthenium(II), Ru(TMP) (N2)2 was synthesized according to the literature procedure (14,15). Carbon monoxide and ethylene impurities in acetylene (Matheson) were removed by three freeze-pump-thaw cycles at -130°C using an n-pentanelliquid N2 slush-bath.…”

“…(7,9,14), which is thus clearly more stable thermodynamically than the C2H4 complex or the Ru(TMP)(N2),, complexes ( n = 1 , 2), the latter readily being formed under N2 atmospheres (14,15). Under the conditions of catalytic 0,-or aerobic-epoxidation of alkenes using Ru(TMP)L2 precursors ( L = MeCN, THF), the catalysis operating via the Ru(TMP)(O), species (7-lo), there will be a competition between O2 and alkene for the metal site.…”