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

Abstract

A series of ruthenium(II) acetonitrile, pyridine (py), carbonyl, SO 2 , and nitrosyl complexes [Ru(bdmpza)(O 2 CR)(L)(PPh 3 )] (L ) NCMe, py, CO, SO 2 ) and [Ru(bdmpza)(O 2 CR)(L)(PPh 3 )]BF 4 (L ) NO) containing the bis(3,5-dimethylpyrazol-1-yl)acetato (bdmpza) ligand, a N,N,O heteroscorpionate ligand, have been prepared. Starting from ruthenium chlorido, carboxylato, or 2-oxocarboxylato complexes, a variety of acetonitrile complexes [Ru(bdmpza)Cl(NCMe)(PPh 3 )] (4) and [Ru(bdmpza)(O 2 CR)(NCMe)(PPh 3 )] (R ) Me (5a), R ) Ph (5b)), as well as the pyridine complexes [Ru(bdmpza)Cl(PPh 3 )(py)] ( 6) and [Ru(bdmpza 9a, 9b). In the same way, the corresponding sulfur dioxide complexes [Ru(bdmpza)(O 2 CMe)(PPh 3 )(SO 2 )] (10a) and [Ru(bdmpza)(O 2 CPh)(PPh 3 )(SO 2 )] (10b) were formed in a reaction of the carboxylato complexes with gaseous SO 2 . None of the 2-oxocarboxylato complexes [Ru(bdmpza)(O 2 C(CO)R)(PPh 3 ) 2 ] (R ) Me (3a), Et (3b), Ph (3c)) showed any reactivity toward CO or SO 2 , whereas the nitrosyl complex cations [Ru(bdmpza)(O 2 -CMe)(NO)(PPh 3 )] + (11) and [Ru(bdmpza)(O 2 C(CO)Ph)(NO)(PPh 3 )] + (12) were formed in a reaction of the acetato 2a or the benzoylformato complex 3c with an excess of nitric oxide. Similar cationic carboxylato nitrosyl complexes 14c)) are also accessible via a reaction with NO[BF 4 ]. X-ray crystal structures of the chlorido acetonitrile complex [Ru(bdmpza)Cl(NCMe)(PPh 3 )] (4), the pyridine complexes [Ru(bdmpza)(O 2 CMe)(PPh 3 )(py)] (7a) and [Ru(bdmpza)(O 2 CC(O)Et)(PPh 3 )(py)] (8b), the carbonyl complex [Ru(bdmpza)(O 2 CPh)(CO)(PPh 3 )] (9b), the sulfur dioxide complex [Ru(bdmpza)(O 2 -CPh)(PPh 3 )(SO 2 )] (10b), as well as the nitrosyl complex [Ru(bdmpza)(O 2 C(CO)Me)(NO)(PPh 3 )]BF 4 (14a), are reported. The molecular structure of the sulfur dioxide complex [Ru(bdmpza)(O 2 CPh)(PPh 3 )(SO 2 )] (10b) revealed a rather unusual intramolecular SO 2 -O 2 CPh Lewis acid-base adduct.

Bis(3,5‐dimethyl‐4‐vinylpyrazol‐1‐yl)acetic Acid: A New Heteroscorpionate Building Block for Copolymers that Mimic the 2‐His‐1‐carboxylate Facial Triad

“…All other solvents were used as purchased without further purification and degassed prior to use. Bis(3,5-dimethylpyrazol-1-yl)-methane, [18] bis(3,5-dimethyl-4-formylpyrazol-1-yl)methane, [19] [Ru(bdmpza)Cl(PPh 3 ) 2 ], [21] [Ru(bdmpza)(O 2 CCH 3 )(PPh 3 )], [5,23] [MnBr(CO) 5 ], [24] [ReBr(CO) 5 ], [24] [RuCl 2 (PPh 3 ) 3 ], [25] and N-oxalylglycine hydrate [26] were synthesised according to literature. …”

“…Examples of hemilabile carboxylato and 2-oxocarboxylato ruthenium complexes bearing the Hbdmpza ligand as model complexes for 2-oxoglutarate (2-OG) dependent iron enzymes have been published by our group before. [5,23] With our new ligand Hbdmvpza (4) which is suitable for copolymerisation but also capable of binding ruthenium with the κ 3 -N,N,O motif, a door to imprinted polymer techniques might be opened (Scheme 5).…”

“…The content of iron is determined by AAS to 0.165 mmol g -1 . [5,23] (303 mg, 0.452 mmol) in CH 2 Cl 2 is added N-oxalylglycine (75.0 mg, 0.510 mmol). The mixture is stirred 5 h at ambient temperature.…”

Transition metal complexes bearing a 2,2-bis(3,5-dimethylpyrazol-1-yl)propionate ligand: one methyl more matters

“…Usually these values are in a range of 1254 to 1296 cm -1 and 1096 to 1128 cm -1 respectively. [28][29][30][31][32][33][34] The result of a single crystal structure analysis of complex 11 is depicted in Fig. 8.…”

Development of ruthenium-based complexes as anticancer agents: toward a rational design of alternative receptor targets

“…Since then, several Ru half-sandwich complexes have been synthesized (Komiya and Hurano coordinating ligands to possibly mimic the feature of the best anticancer complex called cisplatin, which is characterized with two units of NH 2 ligand. In addition to the complexes from the Sadler research members that most often characterized heterocyclic nitrogen-containing ligands, many other researchers have equally characterized the Ru-based complexes that contained 1,10-phenanthroline (Hara et al 2001, Byabartta et al 2003, Himeda et al 2004, Nakabayashi et al 2004, Canivet et al 2005, Małecki et al 2009, Al-Lawati et al 2010, Chen et al 2010, bipyridine (Pruchnik et al 1999, Mitsopoulou et al 2007, Wei et al 2008, Tomaz et al 2012, terpyridine (Koizumi et al 2003, Bolink et al 2005, Sharma et al 2005, Zhou and Harruna 2005, Etienne and Beley 2006, Hofmeier et al 2006, Goze et al 2007, Rajalakshmanan and Alexander 2007, Jain et al 2009), and bis(pyrazoly-l-yl) (Burns et al 1998, Kopf et al 2006, Tampier et al 2008, Zhao et al 2009, Blasberg et al 2010, Türkoglu et al 2012 for different purposes, such as electrochemiluminescence, catalyst, photochemical, and anticancer complexes. However, the application of these type of Ru complexes as potential anticancer is predominant (Concepcion et al 2000, Peacock et al 2007a, Sun et al 2009, Zhu and Holliday 2010,...…”