Ruthenium Carbene, Vinylidene, and Allenylidene Complexes with a Bis(3,5-dimethylpyrazol-1-yl)acetato Heteroscorpionate Ligand

Abstract

A series of neutral ruthenium(II) carbonyl, carbene, vinylidene, and allenylidene complexes [Ru(bdmpza)(Cl)(L)(PPh3)] (L = C(OR‘)R, CCHR, CCCR2, CO) containing the bis(3,5-dimethylpyrazol-1-yl)acetato (bdmpza) ligand, an N,N,O heteroscorpionate ligand, have been prepared. Treatment of [Ru(bdmpza)(Cl)(PPh3)2] (1a) with a variety of alkynes HC⋮CR (R = Ph, Tol, Pr, Bu) afforded the vinylidene complexes [Ru(bdmpza)(Cl)(CCHR)(PPh3)] (2a−d). The carbonyl complex [Ru(bdmpza)(Cl)(CO)(PPh3)] (3) is formed via oxidative or acid-induced degradation pathways from the vinylidene complexes. Reaction of 1a with the hydroxy-functionalized alkynes HC⋮C(CH2) n OH (n = 2, 3) yielded the cyclic Fischer type carbene complexes (4a) and (4b). The ruthenium(II) allenylidene complexes [Ru(bdmpza)(Cl)(CC CR2)(PPh3)] (5a, R = Ph; 5b, R = Tol) were prepared by the reaction of 1a with propargyl alcohols HC⋮CC(R)2OH via the vinylidene intermediates [Ru(bdmpza)(Cl)(CCHCR2OH)(PPh3)]. X-ray crystal structures of one structural isomer of the vinylidene complex [Ru(bdmpza)(Cl)(CCHTol)(PPh3)] (2b), the carbonyl complex [Ru(bdmpza)(Cl)(CO)(PPh3)] (3), the carbene complex (4b - I), and two structural isomers of [Ru(bdmpza)(Cl)(CCCPh2)(PPh3)] (5a - I and 5a-II) are reported.

Synthesis, structural and spectroscopic characterization and biomimetic properties of new copper, manganese, zinc complexes: Identification of possible superoxide-dismutase mimics bearing hydroxyl radical generating/scavenging abilities

“…Their analytical and spectroscopic data correspond to those reported in the literature [39,40]. To a stirred solution of L 1 (0.59 g, 1.0 mmol) in dichloromethane, CuCl 2 ·2H 2 O (0.342 g, 2.0 mmol), dissolved in methanol, was added.…”

Synthesis, Structure, and Reactivity of Ruthenium Carboxylato and 2-Oxocarboxylato Complexes Bearing the Bis(3,5-dimethylpyrazol-1-yl)acetato Ligand

“…In contrast, so far most molecular structures showed a chlorido ligand trans to the carboxylato donor of the bdmpza ligand. 3,4 The complex [Ru(bdmpza)(O 2 CPh)(NCMe)(PPh 3 )] (5b) does form two isomers which show a rather similar pattern in the NMR spectra. The acetonitrile signals have been assigned for both isomers ( 1 H NMR: 2.23 and 1.92 ppm; 13 C NMR: 2.23, 124.7, and 3.56, 124.1 ppm).…”

One-pot Synthesis of Octyne-Ruthenium on Carbon Nanoparticles

“…Herein, it was reasonable to conclude the successful production of our process. ICMSNT 2017 5 The structure of pure carbon nanoparticles and C/Ru/Oct were then examined by FTIR spectrum and compare with CPNs as shown in figure 3. For the CPNs, a characteristic peak at 1160cm −1 was assigned to C-C bonds.…”

“…Recently, many reports have been generally successfully prepared alkyl vinylidene -linkage to ruthenium core using the special coordinating ligand for example terminal alkyne [1][2][3][4][5] or some vinyl aromatic [6][7]. It is confirmed that alkyne fragments around the metal core do not only functions as protecting ligands promoting the stability of the nanoparticles but also enhances some optical and fluorescence characteristic via the pi-bond interaction between methylene and metal core [8].…”