Intramolecular dealkylation of chelating diamines with Ru(ii) complexes

Abstract

N,N, N',N'-Tetraethylethylenediamine undergoes simple or double intramolecular dealkylation reactions in the presence of the complexes [RuCl2(diene)]n (diene = cod, nbd) or trans-[RuCl2(diene)(morfoline)2 at 80 degrees C to afford chelating amine ligands which contains one or two N-H functionalities.

Synthesis and reactivity of iridium complexes with pyridine and piperidine ligands: models for hydrodenitrogenation

“…See http://www.rsc.org/suppdata/dt/b4/b406949h/ At room temperature Py or iQ immediately displace pip from 3 to generate 1 and 2, respectively. On the other hand, under a slow stream of carbon monoxide at room temperature, only one piperidine ligand of 3 is displaced by CO to produce a stable monopiperidine derivative [Ir(H) 2 ( 1 N-pip)(CO)(PPh 3 ) 2 ]PF 6 (8). The 1 H NMR spectrum displays two distinct high-field signals at −8.0 ppm, (triplet of doublets, J HP = 17.2 Hz, J HH = 4.8 Hz) and −18.8 ppm, (triplet of doublets, broadened possibly by the N quadrupolar effect or by interaction with the proton on NH) while the 31 P NMR spectrum consists of a singlet at 15.1 ppm.…”

“…Data reduction were performed using TEXSAN 25 crystallographic software package of the Molecular Structure Corporation, whereas refinement calculations and graphical representations were made using SHELXTL-NT. 24 CCDC reference numbers 213808 (1), 213809 (2) and 213810 (8).…”

“…[3][4][5] Modelling work has primarily focused on the coordination of N-heterocycles on mononuclear metal centres, on the homogeneous catalytic hydrogenation of N-aromatic compounds and on C-N bond activation. [5][6][7][8] As part of the organometallic modelling of the chemisorption and subsequent steps involved in HDN, it is important to study the coordination and reactivity of pyridines and of their hydrogenated derivatives with metal centres. In this paper, we report the synthesis and reactivity of stable  1 -N-bonded complexes of the type [Ir(H) 2 ( 1 -N-L) 2 (PPh 3 ) 2 ]PF 6 , L = py (1), iQ (2), and pip (3); the X-ray structures of complexes 1, 2 and of a carbonyl derivative of 3 are also described.…”

Synthesis and X-ray structure of ruthenium bis(acetylacetonate)(N,N,N′,N′-tetramethylethylenediamine)

“…The successful synthesis begins with trans-RuCl 2 (tmed) 2 , [8][9][10] which readily exchanges both chloride ligands for two acetylacetonate ligands during reflux in toluene under N 2 in the presence of acetylacetone and triethylamine. The literature syntheses of RuCl 2 (tmed) 2 involve the reaction of [RuCl 2 (olefin)] 2 (olefin = cyclooctadiene or norbornadiene) with 2-3 atm of H 2 in the presence of tmed.…”

Atom-Economical Synthesis of the Versatile Ruthenium Precursor [TpRuCl(COD)] (Tp = Hydrotris(pyrazol-1-yl)borate) Discloses a Diamine Ligand Dealkylation Process

“…It also resembles the structure of trans-[RuCl 2 (COD)(EtNHCH 2 CH 2 NHEt)]. 18 The most relevant feature of the structure of 2 is the fact that the Ru(1)−N(1) and Ru(1)−N(2) bond distances have significantly different values, 2.259(2) and 2.163(2) Å, respectively. This difference in the Ru−N separations involving secondary and tertiary nitrogen atoms has also been observed in the structure for the complex trans-[RuCl 2 (NBD)(Et 2 NCH 2 CH 2 NHEt)].…”