Unexpected isomerism in “[Pd(2,9-dimethylphenanthroline)X2]” (X = Cl, Br, I) complexes: a neutral and an ionic form exist

Abstract

Complexes of composition "[Pd(2,9-dimethylphenanthroline)X(2)]" (X = Cl, Br, I) have long been known and they are used as precursors for the synthesis of other derivatives or as catalysts. In the previous literature, they have invariably been described as neutral square planar complexes, but we have found that a second ionic isomer also exists, having composition [Pd(Neoc)(2)X](2)[Pd(2)X(6)], and that the formation of this isomer occurs under a wider range of conditions than that of the neutral one. Retrospectively, the ionic isomer had surely been obtained in most previous reports even if formation of the neutral one was claimed.

Electron Delocalization of Mixed‐Valence Diiron Sites Mediated by Group 10 Metal Ions in Heterotrimetallic Fe‐M‐Fe (M=Ni, Pd, and Pt) Chain Complexes

“…It should be noted that a ratio of 1:6 (Ni II /Fe II ) was used to avoid the formation of the homotrinickel string complex. For the preparation of 2 and 3 , [MCl 2 (MeCN) 2 ] salts (M=Pd and Pt) were used, replacing the corresponding anhydrous salts MCl 2 for ease of synthetic operations . Compound 2 was prepared based on similar synthetic procedures as those for 1 , whereas an extended reaction time (≈3 h) was applied.…”

“…[18b] For 1,am ixture of anhydrous FeCl 2 , Hdpa (dipyridylamine), and NiCl 2 was heated with naphthalene at 200 8Cf or approximately 1h.S olid tBuOK wast hen added to deprotonate the Hdpa ligand, and the mixture was continually heateda tr eflux temperature (200 8C) for 10 min. After that, the resultingm ixture was cooled and treated with hexane to dissolve naphthalenea nd to precipitate the target product, which was further extracted by CH 2 Cl 2 .I ts hould be noted that ar atio of 1:6( Ni II /Fe II )w as used to avoid the formationo ft he homotrinickel string complex.F or the preparation of 2 and 3, [MCl 2 (MeCN) 2 ]s alts (M = Pd and Pt) were used, [19] replacing the corresponding anhydrous salts MCl 2 for ease of synthetic operations. [20] Compound 2 was prepared based on similars ynthetic procedures as those for 1,w hereas an extended reaction time ( % 3h)w as applied.…”

Coordinative Flexibility of a Thiophenolate Oxazoline Ligand in Nickel(II), Palladium(II), and Platinum(II) Complexes

“…General Procedures: LiS‐Phoz was synthesized according to our previously published protocol 2. [PdCl 2 (NCMe) 2 ]16 was synthesized according to a literature procedure. All other precursors and chemicals were purchased from commercial sources and were used without further purification.…”

Mercaptoaryl‐Oxazoline Complexes of Palladium and Their High Activities as Catalysts for Suzuki–Miyaura Coupling Reactions in Water

“…LiS‐Phoz, [{PdCl(S‐Phoz)} 2 ] ( 1 ), and [PdCl(S‐Phoz)(PPh 3 )] ( 7 ) were synthesized according to our previously reported protocols , . The [PdX 2 (MeCN) 2 ] precursors and the IMes NHC ligand were synthesized according to literature procedures . All other chemicals were obtained from commercial sources and used without further purification.…”