Multidentate aryloxide and oxo-aryloxide complexes of antimony: synthesis and structural characterization of [η4-N(o-C6H4O)3]Sb(OSMe2), {{[η3-N(o-C6H4OH)(o-C6H4O)2]Sb}2(µ2-O)}2 and {[η3-PhN(o-C6H4O)2]Sb}4(µ3-O)2

Abstract

Antimony compounds that feature multidentate aryloxide ligands, namely [eta4-N(o-C6H4O)3]Sb(OSMe2), {{[eta3-N(o-C6H4OH)(o-C6H4O)2]Sb}2(mu2-O)}2, and {[eta3-PhN(o-C6H4O)2]Sb}4(mu3-O)2 have been synthesized from N(o-C6H4OH)3 and PhN(o-C6H4OH)2 and structurally characterized by X-ray diffraction. While [eta4-N(o-C6H4O)3]Sb(OSMe2) exists as a discrete mononuclear species, the oxo complexes {{[eta3-N(o-C6H4OH)(o-C6H4O)2]Sb}2(mu2-O)}2 and {[eta3-PhN(o-C6H4O)2]Sb}4(micro3-O)2 are multinuclear. Specifically, the dinuclear fragment {[eta3-N(o-C6H4OH)(o-C6H4O)2]Sb}2(mu2-O)} exists in a dimeric form due to the bridging oxo ligand participating in an intermolecular hydrogen bonding interaction, while the dinuclear fragment {[eta3-PhN(o-C6H4O)2]Sb}2(mu-O) exists in a dimeric form due to the bridging oxo ligand serving as a donor to the antimony of a second fragment. The structures of {{[eta3-N(o-C6H4OH)(o-C6H4O)2]Sb}2(mu2-O)}2 and {[eta3-PhN(o-C6H4O)2]Sb}4(mu3-O)(2), therefore, indicate that an oxo ligand bridging two Sb(III) centers is sufficiently electron rich to serve as both an effective hydrogen bond acceptor and as a ligand for an additional Sb(III) center.

Synthesis and structural characterization of tris(phenolate)amine complexes of antimony derived from

“…While the overall structure of ½j 4 -NðCH 2 Ar Bu t 2 OÞ 3 - [11], the magnitude of the Sb-OSMe 2 interactions are significantly different. Specifically, the Sb-OSMe 2 bond length for ½j 4 [17].…”

“…1. The geometry of the five-coordinate antimony center is square pyramidal, with the stereochemically active lone pair occupying the coordination site trans to the axial nitrogen donor, analogous to that of [j 4 -N(o-C 6 H 4 O) 3 ]Sb(OSMe 2 ) [11,16]. Neglecting the Sb-OSMe 2 interaction, the geometry of the ½j 4 -NðCH 2 Ar Bu t 2 OÞ 3 Sb moiety approximates to a ''cis-divacant octahedron'', with bond angles close to 90°and 180°.…”

“…The coordination chemistry of antimony alkoxide and aryloxide compounds is, however, complex, as illustrated by the structural variations that are observed for [Sb(OMe) 3 ] n [5], [Sb(OPr i ) 3 ] 2 [6], [Sb(OSiMe 3 ) 3 ] 2 [7,8], Sb(OC 6 H 3 -2,6-Me 2 ) 3 [9], and [Sb 2 (OCH 2 CH 2 O) 3 ] n [10]. As part of an effort to investigate the reactivity of well-defined antimony aryloxide compounds, we recently described the first application of the tris(phenol)amine N(o-C 6 H 4 OH) 3 to antimony chemistry [11]. In this paper, we describe an extension of these investigations by employing tris(3,5-dit-butyl-2-hydroxybenzyl)amine, NðCH 2 Ar Bu t 2 OHÞ 3 [12], with the notion that the methylene spacer between the nitrogen and the phenol group would modulate the electronic and geometric properties of the antimony center, such as its Lewis acidity.…”

“…We previously synthesized the antimony complex [j 4 -N (o-C 6 H 4 O) 3 ]Sb via the reaction of Sb(OEt) 3 with N(o-C 6 H 4 -OH) 3 [11]. The related complex ½j 4 -NðCH 2 Ar Bu t 2 OÞ 3 Sb is likewise obtained upon treatment of Sb(OEt) 3 with NðCH 2 Ar Bu t 2 OHÞ 3 (Scheme 1) [13].…”

The Anhydride Route to Group 15/16 Ligands in Oligomeric and Polymeric Environments: From Metal Complexes to Supraionic Chemistry

“…[6,7] The efforts to be described add on to the research area of Group 15/16 anions for which numerous compounds containing the structural fragments [Group 15 elementGroup 16 element E metal] are known (e.g., N-E, [8][9][10] P-E, [11][12][13][14] As-E, [15][16][17][18][19] Sb-E, [20][21][22][23] Bi-E [24][25][26][27][28] ).…”