Role of Cation−Anion Interactions in Ionic Complexes Containing [Pd{C₆H₃(CH₂NMe₂)₂-2,6}(OH₂)]⁺ and [{Pd(C₆H₃(CH₂NMe₂)₂-2,6)}₂(μ-Cl)]⁺ Cations

Abstract

The reaction of [PdCl{C6H3(CH2NMe2)2-2,6}] ([PdCl(NCN)]) with either the sodium or silver salts of the borate anions [B{C6H4(SiMe3)-4}4]- and [B(C6H4{SiMe2(CH2CH2C6F13)}-4)4]- under various reaction conditions resulted in the exclusive formation of the respective dinuclear [{Pd(NCN)}2(μ-Cl)][B{C6H4(SiMe2R)-4}4] salts 4a (R = Me) and 4b (R = CH2CH2C6F13). When using BF4 -, both dinuclear [{Pd(NCN)}2(μ-Cl)]BF4 (4c) and mononuclear [Pd(NCN)(OH2)]BF4 (5c) could be obtained. The molecular structure of 5c showed the presence of hydrogen-bridging interactions between coordinated H2O molecules and the fluorine atoms of BF4 -. Attempts to isolate complexes of the type [Pd(NCN)(OH2)][B{C6H4(SiMe2R)-4}4] were unsuccessful. This has been ascribed to a difference in stabilization of the respective mono- and dinuclear cations by the borate anions BF4 - and [B{C6H4(SiMe2R)-4}4]-, respectively. The conclusions are supported by DFT calculations.

Palladacycles with C,N-bidentate and N,C,N′-tridentate ligands: Structures, spectral study and catalytic methanolysis of P S pesticides

“…The five-membered metallacycles are puckered in the same direction, with PdeN1eC7eC2 and PdeN2eC10eC6 torsion angles of À32.72 and À61.72 , respectively. The bond lengths and angles (see Table 1) are in good agreement with those in [Pd(NCN)(OH 2 )]BF 4 [7].…”

Mononuclear versus dinuclear palladacycles derived from 1,3-bis(N,N-dimethylaminomethyl)benzene: Structures and catalytic activity

“…The five membered metacycles are puckered in the same direction, with Pd (1)-N(1)-C(7)-C(2) and Pd(1)-N(2)-C(10)-C(6) torsion angles of 28.17°and 57.97°, respectively. The Pd-N and Pd-C bond lengths are similar to those generally encountered in NCN pincer palladium(II) complexes [10,21,22], but they are shorter than those in the C,N-ortho coordinated palladacycles [14,19].…”

Solid‐State Structural Characterization of Cutinase–ECE‐Pincer–Metal Hybrids

“…Due to this, the second chloride is assumed to be disordered in the bulk solvent region. It is important to note that the formation of m-halide-bridged dinuclear pincer-metal complexes has been observed for small-molecule analogues before [50,51] and was found to be an intrinsic property of the NCN-pincer-metal cationic moieties (in which the metal is platinum or palladium) under halide-poor reaction conditions. The corresponding small-molecule structures of…”

“…+ dinuclear NCN-pincer-palladium complexes have slightly different Pd2-Cl1-Pd1 angles (134.808 [50] and 121.118 [51] ) and torsion angles (À95.788 [50] and À61.328 [51] ). These observations show that the m-halide-bridged dimer formation can also occur with cutinase-pincer hybrids in which the covalently anchored cutinase molecules act as giant para-substituents for each of the NCN-pincer-platinum cations.…”