Conjugate Base of a Secondary Phosphine Selenide [P(Se)(OⁱPr)₂]⁻as the Bridging Unit for the Construction of Heterometallic Fe(II)−Hg(II)/Cd(II) Complexes

Abstract

Reactions of perchlorate salts of Hg(II)/Cd(II) with [CpFe(CO)(2)P(Se)(O(i)Pr)(2)] (denoted as L) produced dicationic clusters [HgL(2)](ClO(4))(2), 1; [HgL(3)](ClO(4))(2), 2; and [CdL(3)(H(2)O)](ClO(4))(2), 11. However, the reactions of L with Hg(II)/Cd(II) halides yielded neutral complexes. For instance, HgI(2) produced [Hg(3)I(6)L(2)], 3, or [HgI(2)L(2)], 4, depending on the metal-to-ligand ratio used. Reaction of L with any of the Hg(II)/Cd(II) halides in a 1:1 ratio produced neutral clusters [HgX(mu-X)L](2) (M = Hg; X = Cl, 5; Br, 6; I, 7; M = Cd; X = Cl, 8; Br, 9; I, 10). Thus, variation of the M-to-L ratio made it possible for the formation of compounds with different metal/ligand stoichiometries only when ClO(4)(-) and I(-) salts of Hg(II) were used. Single-crystal X-ray crystallography revealed that two and three L units were connected to a Hg(II) via its Se atom in 1 and 2, respectively, whereas Hg(II) in 4 was connected to two "I" and two "L" units. An L (through its Se) and a terminal halogen were attached to each of the Hg(II)'s of the Hg(2)X(2) parallelogram core in 5 and 6. The cadmium complex 8, with a Cd(2)Cl(2) parallelogram core, was isostructural with the mercury complex 5. Although bonding and connectivity in 8 were similar to those in 9 and 10, the conformation of the bulky L ligands was unusually syn in 9 and 10, unlike the anti orientation in 5, 6, and 8. The syn conformation of L was also observed in compounds 1 and 2. Secondary interactions, namely, Se...Se interaction, the X...H-C type of H-bonding (X = halogen or Se), and pi-stacking, revealed in the structures played a role in determining the ligand conformation. The [P(Se)(O(i)Pr)(2)](-), the conjugate base of secondary phosphine selenide [HP(Se)(O(i)Pr)(2)], acted as a bridge with P bonded to Fe and Se bonded to Hg (or Cd) in these heterometallic clusters. Compound 5 further demonstrated a longer P-Se bond in the secondary phosphine selenide compared to that in isostructural, tertiary phosphine selenide metal complexes.

Protolytic Cleavage of Hg–C Bonds Induced by 1-Methyl-1,3-dihydro-2H-benzimidazole-2-selone: Synthesis and Structural Characterization of Mercury Complexes

“…In addition to [H­(sebenz­im Me )] 4 ­HgCl 2 being of significance because its existence demonstrates that a mercury center can accommodate four selenium L-type donor ligands, the tris complex, [H­(sebenz­im Me )] 3 ­HgCl 2 , is of interest because structurally characterized mercury compounds with three L-type selenium donors are also uncommon. Thus, compounds with a HgSe 3 motif are typically polynuclear selenide or selenolate derivatives; there are, nevertheless a few structurally characterized mononuclear compounds that contain mercury coordinated to three dative L-type selenium ligands, of which [(MeImSe) 3 HgCl]­Cl, {[N­(CH 2 CH 2 SePh) 3 ­Hg­(κ 2 -NO 3 )}­(NO 3 ), and {[CpFe­(CO) 2 P­(OPr i ) 2 Se] 3 Hg}­(ClO 4 ) 2 , are illustrative.…”

Fluorescent, Theoretical and Structural Investigations on [Me4bim][CdCl4] (Me4bim = 1,1′,3,3′-tetramethyl-2,2′-bi-1H-imidazolium)

“…The Cd-Cl bond distances are between 2.4677(6) Å and 2.4992(6) Å with a mean value of 2.4844(7) Å, which is comparable with data documented previously. [12][13][14][15] The dihedral angle of two anions, the charge of the Me 4 bim moiety should be +2, as in the cases found in the literature. [16][17][18][19][20] The Me 4 bim moieties are interconnected to the [CdCl 4 ] 2− anions via C-H•••Cl hydrogen bonds, yielding a supramolecule, as shown in Fig.…”

“…The Cd-Cl bond distances are between 2.4677(6) Å and 2.4992(6) Å with a mean value of 2.4844(7) Å, which is comparable with data documented previously. [12][13][14][15] The dihedral angle of two (7) Cl(2)-Cd(1)-Cl(4) 105.77(2) Cd(1)-Cl (2) 2.4677 (6) Cl (1) The solid-state emission spectra of 1 were measured at room temperature. The emission spectra of 1 are shown in Fig.…”

D-A-D type molecules based on dibenzophosphole-chalcogenides and triphenylamine moieties; effects of chalcogenide atoms on their photochemical properties

“…3,[6][7][8][9][10] Because of specific coordinating and chalcogen binding nature of phosphorus atom, phosphole acts as a binding site for various heavy atoms. [11][12][13] Phosphole-chalcogenides can also be the -building block with isoelectric nature. Since limited number of studies have been conducted for elucidating nature of phosphole-chalcogenides, [14][15][16][17] systematic synthetic study on a series of phosphole-chalcogenides and their characterization are still demanded.…”