Complexation of methylparathion and bis(2-hydroxyethyl)sulfide by the tridentate lewis acid [(o-C6F4Hg)3]

Abstract

The interaction

Complexation of [9]Thiacrown-3 and 1,3,5-Trithiane with Cyclic Trimeric Perfluoro-o-phenylenemercury. Synthesis and Structures of the First Complexes of Crown Compounds with an Anticrown

“…The Hg(1)−S(1) and Hg(2A)−S(2) distances in 2 are 3.139(2) and 3.194(2) Å, respectively, which is substantially shorter than the sum of the van der Waals radii of mercury (1.73−2.00 Å, 11a,b 2.1 Å 11c ) and sulfur (2.03 Å 11d ) atoms. These Hg−S distances are comparable to the Hg−S bond length (3.138(4) Å) found in the 1:1 complex of 1 with bis(2-hydroxyethyl)sulfide whose sulfur atom is also coordinated in the adduct only to one Hg atom of the anticrown . Interestingly, the planes of the central Hg 3 C 6 rings of the adjacent mercuramacrocycles in 2 are almost perpendicular to each other (the interplane angle is 79.0°).…”

“…In the previously reported 2:1 complex of 1 with tetrathiafulvalene (TTF), the molecule of a sulfur-containing guest is also sandwiched by two anticrown molecules; however in this adduct only two Hg centers of each molecule of 1 interact with the sulfur atoms (the Hg−S distances span the range 3.467(5)−3.533(5) Å). In the 1:2 complex of 1 with methylparathion, having a bipyramidal structure, the Hg−S bond lengths are in the range 3.278(3)−3.651(3) Å (av 3.42 Å), and in the 1:4 complex of 1 with dimethyl sulfide they are 3.198(7)−3.508(7) Å (av 3.37 Å) 2 ORTEP representation of the molecular structure of complex 3A with thermal ellipsoids drawn at the 50% probability level. 2 Selected Bond Lengths (Å) and Angles (deg) in the Two Independent Molecules 3A/3B Bond Lengths Hg(1)−S(1) 3.192(4)/3.211(4) C(37)−S(1) 1.822(17)/1.846(16) Hg(2)−S(1) 3.445(4)/3.399(4) C(42)−S(1) 1.800(17)/1.835(17) Hg(3)−S(1) 3.337(4)/3.385(4) C(38)−S(2) 1.804(16)/1.790(16) Hg(4)−S(2) 3.181(4)/3.123(4) C(39)−S(2) 1.825(18)/1.837(17) Hg(5)−S(2) 3.491(4)/3.543(4) C(40)−S(3) 1.827(19)/1.820(16) Hg(6)−S(2) 3.632(4)/3.590(4) C(41)−S(3) 1.884(17)/1.836(16) Hg(5)−S(3) 3.394(5)/3.500(5) Bond Angles C(42)−S(1)−C(37) 104.4(9)/104.3(9) C(40)−C(39)−S(2) 117.7(13)/114.4(12) C(38)−S(2)−C(39) 107.2(8)/106.2(9) C(39)−C(40)−S(3) 116.8(13)/114.5(12) C(40)−S(3)−C(41) 106.7(8)/106.2(8) C(42)−C(41)−S(3) 117.5(13)/120.6(13) C(38)−C(37)−S(1) 116.4(13)/115.2(12) C(41)−C(42)−S(1) 117.7(13)/119.1(13) C(37)−C(38)−S(2) 116.1(11)/116.5(12) …”

Lewis Acidic Behavior of Fluorinated Organomercurials

“…The Hg···S bonds (3.571(3) and 3.543(7) Å) are slightly longer than those observed in [ 7 ·(Me 2 S) 2 (μ 3 -Me 2 S) 2 ] for the triply coordinated dimethyl sulfide molecules but remain within the sum of the van der Waals radii. Compound 7 also interacts with bis(2-hydroxyethyl)sulfide to form a 1:1 adduct with a single and relatively short Hg···S bond of 3.14 Å . Several Hg···O interactions also add to the stability of this adduct.…”

Anion Binding Based on Hg3 Anticrowns as Multidentate Lewis Acidic Hosts

“…Here, the ( o -C 6 F 4 Hg) 3 molecule behaves as a three-dentate Lewis acid via its three Hg­(II) centers. On the other hand, we have observed a marked variability in the nature of the interacting LB, including both neutral and anionic species such as benzene (ABELUO), naphthalene (MOXMIV), triphenylene (MOXMOB), corannulene (IXOBAZ), closo -dodecaborate (ACEREF), dimethyl sulfoxide (CAMFOM), methyl parathion (CEJNUB), ferrocene (FANNUE), and nickelocene (FANPAM) via their Cp ligands, nitrate (HIMHUI) and nitrobenzene via the O atoms (REWZID), and dimethylsulfide (UKUQEW), carbon disulfide (PAGLIT), coordinated pentaphosphole (JOVHOT) and pentarsolyl (JOVVOH), and polyynes through their triple bonds (JEGLEN) . In Figure , two selected examples are shown in which the LBs are dimethylketone and chloride (MUPXAW and YOLCAG, respectively).…”