Trivalent Antimony as L-, X-, and Z-Type Ligand: The Full Set of Possible Coordination Modes in Pt–Sb Bonds

Abstract

In the course of our investigations of the coordination chemistry of trivalent antimony (Sb) compounds, we studied heteronuclear complexes formed in reactions of the compounds RSb(pyS) 2 (R = pyS, Ph; pyS − = pyridine-2-thiolate) with [Pt(PPh 3 ) 4 ], i.e., complexes [(R)Sb(μ-pyS) 2 Pt-(PPh 3 )] (R = pyS, 1; R = Ph, 2). The reaction of 1 with o-chloranil proceeds cleanly with elimination of 2,2′-dipyridyl disulfide and formation of the salt), which features the cation 3 + . The charge-neutral, unsymmetrically substituted compound [(PPh 3 )Pt(μ-pyS) 2 Sb(μ-pyS) 2 Pt(κS-pyS)] ( 4) can be accessed by the reaction of 3 + with LipyS. The oxidation of 2 with o-chloranil furnishes the complex [(κ-O,O-C 6 Cl 4 O 2 )PhSb(μ-pyS) 2 Pt(PPh 3 )] ( 5). The oxidation of 1 with PhICl 2 afforded the paddlewheel-shaped complex [Sb(μ-pyS) 4 PtCl] (6). Moreover, compound 6 was obtained by the reaction of Sb(pyS) 3 with [PtCl(pyS)-(PPh 3 )]. The polarization of Pt−Sb bonds of compounds 1−6 was investigated by natural localized molecular orbital (NLMO) calculations, which suggest X-type ligand character (covalent Pt−Sb bonds) for 1 and 2, whereas the Sb ligand of 6 reflects Z-type character (dative Pt→Sb bonds). In 3 + , 4, and 5, high contributions of the reverse, i.e., L-type (dative Pt←Sb bonds), were observed. In conjunction with the results of NLMO analyses, 121 Sb Mossbauer spectroscopy proves that complexes 1−6 represent essentially trivalent Sb complexes with either a free lone pair (LP) at the Sb atom (1, 2, and 6) or LP character involved in L-type Pt←Sb coordination (3 + , 4, and 5).

Deciphering the Sb4O5Cl2–MXene Hybrid as a Potential Anode Material for Advanced Potassium-Ion Batteries

“…The schematic representations in Figure a and Table S1 exhibit the crystal structure and lattice parameters of Sb 4 O 5 Cl 2 ( P 21/ c space group), in which the Sb centers occupy two kinds of crystallographic positions (Sb1 and Sb2) with a distinct coordination polyhedron around each Sb (Figure b). , The Sb1 centers are concatenated with four O atoms in trigonal bipyramid-type (SbO 4 E) geometry, with one of the equatorial corners of Sb occupied by a lone electron pair. Meanwhile, the Sb2 sites are coordinated in tetrahedral-type geometry (SbO 3 E) to O atoms where the lone electron pair is located in one of the four corners of Sb2 centers .…”

Hidden Heterometallic Interaction Emerging from Resonant Inelastic X-ray Scattering in Luminescent Tb–Pt Molecules

“…Thus, heterometallic interactions also exert an important influence on the physical properties of heterometallic complexes. Considerable efforts have thus been devoted to the formation of various intermetallic interactions. − Although high-resolution X-ray diffraction analysis can provide insight into the electron density of bonds, theoretical calculations are widely conducted for examining intermetallic interactions. − …”

Untitled

“…It is stable and polar [3]. Amide bonds are commonly utilized in organic synthesis, medicinal chemistry, and agrochemicals, but they can also be used in other fields [4][5][6]. It is molecule acts as potent metal ion chelate, due to its oxygen and nitrogen atoms [7,8].…”