Di-n-octyltin(IV) complexes with 5-[(E)-2-(aryl)-1-diazenyl]-2-hydroxybenzoic acid: Syntheses and assessment of solid state structures by 119Sn Mössbauer and X-ray diffraction and further insight into the solution structures using electrospray ionization MS, 119Sn NMR and variable temperature NMR spectroscopy

Synthesis and Characterization of Archetypal Ladder-Like Dibutyloxotin Cluster Derived from Sterically Encumbered 4-[(E)-2-(4-hydroxy-5-methylphenyl)-1-diazenyl]benzoate

“…Toluene was distilled from sodium benzophenone ketyl [14]. 4-[(E)-2-(4-hydroxy-5-methylphenyl)-1-diazenyl]benzoic acid (LHH 0 ) was prepared by reacting p-carboxybenzenediazonium chloride with o-cresol in alkaline solution under cold conditions by the method described in earlier reports from our group [13,15]. Carbon, hydrogen and nitrogen analyses were performed with a Perkin Elmer 2400 series II instrument.…”

“…More examples of organooxotin clusters, such as alkyl-bridged double-and triple-ladder clusters [6,7], as well as alkyl-bridged Sn 3 O 3 cluster [8], double O-capped clusters [9], organooxotin clusters bridged by an inorganic moiety [10] and organooxotin cluster containing a Sn 5 O 5 ladder [11], are reported in the literature. Among organooxotin clusters, diorganotin clusters of the type {[R 2 Sn(L)] 2 O} 2 were investigated in detail and only a few examples of such complexes with bulkier ligands with flexible diazenyl group have been reported, e.g.,{[Bu 2 Sn(O 2 CC 6 H 4 (OH-2)(N=NC 6 H 4 (X)-5))] 2 O} 2 (X=H, 4-CH 3 , 4-Cl, 4-Br) [12] and {[Oct 2 Sn(O 2 CC 6 H 4 (OH-2)(N=NC 6 H 4 (X)-5))] 2 O} 2 (X=2-OCH 3 , 3-CH 3 ) [13]. These complexes were characterized by spectroscopic methods and crystallographic technique.…”

Synthesis, spectra, and crystal structures of the triorganotin(IV) 5-[(E)-2-(4-methylphenyl)-1-diazenyl]-2-hydroxybenzoates (Me3Sn{O2CC6H3-p-OH[NN(C6H4-4-CH3)]})n, Et3Sn{O2CC6H3-p-OH[NN(C6H4-4-CH3)]}OH2, and Bz3Sn{O2CC6H3-p-OH[NN(C6H4-4-CH3)]}

“…In the structures of 4, 6, and 8, the open side of the Sn-atom actually allows one of the hydroxy oxygen atoms from the 2-hydroxybenzoate moiety of one ligand of a neighboring molecule to form a bridge and coordinate very weakly with the Sn-atom, thereby completing a seventh coordination site in the extended Sn coordination sphere [3,4]. An n Oct 2 Sn(L 1 H) 2 (11) complex also revealed a monomeric six-coordinate structure [5], overall molecular geometry is quite akin to that of the n Bu 2 Sn(LH) 2 complexes discussed above. In line with these developments, a few diorganotin(IV) complexes of the type, R 2 Sn(L a H)(L b H), for example, n Bu 2 Sn-(L 7 H)(L 4 H) (12), n Bu 2 Sn(L 7 H)(L 8 H) (13), and Me 2 Sn-(L 7 H)(L 4 H) (14) have been reported, which furnished the first examples of diorganotin(IV) complexes containing mixed arylazobenzoates and having skew-trapezoidal bipyramidal geometry (Scheme 1, Ib) [6].…”

“…1) ligating diorganotin(IV) centers was developed recently by our group and the mode of coordination is now known. The diorganotin(IV) complexes of the types (i) R 2 Sn(LH) 2 (R = n Bu, n Oct) [1][2][3][4][5], (ii) R 2 Sn(L a H)(L b H) (R = Me, n Bu) [6], and (iii) {[R 2 Sn-(LH)] 2 O} 2 [5,7] are of great interest because of their structural diversity in the crystalline state (Scheme 1) and their interesting biological activity.…”

“…The structures of n Bu 2 Sn(L 1 H) 2 AE 0.5C 6 H 6 (4), n Bu 2 Sn(L 2 H) 2 (5), n Bu 2 Sn-(L 3 H) 2 AE 0.5C 6 H 6 (6), n Bu 2 Sn(L 4-5 H) 2 (7)(8), and n Bu 2 Sn-(L 7-8 H) 2 (9)(10) ligands act as bidentate chelating agents, giving an equatorial plane around the tin atom of four asymmetrically coordinated oxygen atoms. The butyl groups lie in axial positions, thereby completing six-coordination about the Sn-atom, but they are distorted from a true trans position, being pinned back somewhat over the open space left by the equatorial ligands to produce a skew-trapezoidal bipyramidal structure (Scheme 1, Ia).…”