Scientific interest in coordination and organome tallic antimony(V) derivatives is continuously increas ing in the recent two decades [1][2][3][4], which is due to the possibility of using these compounds in diverse areas of fundamental and applied science. These com plexes demonstrate structural variety from monomeric compounds to associated structures and supramolecu lar ensembles [5][6][7][8][9][10]. The antimony compounds are used as components of catalytic systems and reagents in fine organic and organometallic synthesis [11][12][13][14]. In addition, many organoantimony compounds dem onstrate antimicrobial properties and possess antitu mor activity [15][16][17].The chemistry of coordination compounds of o quinone and related ligands is widely developed to the present time [18][19][20] because of the use of their com plexes as model objects in magnetochemical studies, for the construction of molecular switchers, and as catalytic systems. Sterically hindered di o quinones are presently studied to a less extent, although they represent a promising type of ligands for the design of spatially ordered structures [21][22][23][24][25]. The introduction of various binding units (bridging groups) into the di o quinone structure makes it possible to change con siderably the character of mutual effects of the o quinone moieties in the di o quinone molecule and to vary the exchange magnetic interactions between the radical anion semiquinone derivatives from antiferro magnetic to ferromagnetic [22,24].In addition, the most part of studies of the o quinone complexes was carried out with the transi tion metal compounds, whereas the coordination chemistry of nontransition metals with redox active ligands is poorly studied [26]. This is also valid for the antimony o quinone complexes. Among the binuclear antimony complexes (bis(catecholate) derivatives), the derivatives of 4,4' di [(3 methyl 6 tert butyl o benzoquinone) and di o quinones based on 3,6 di tert butyl o benzoquinone containing the ethylene or piperazine bridging groups were described [27][28][29][30].The purpose of the present work is to synthesize antimony(V) bis(catecholate) complexes based on nonsymmetric 1,1' spirobis[3,3 dimethylindane quinone 5,6] (Q Spiro Q) and to study them by IR and NMR spectroscopy and cyclic voltammetry (CV). EXPERIMENTALThe synthesis and study of the properties of the complexes were carried out in evacuated ampules in the absence of oxygen. In all cases, the yields of the target products were higher than 90%. The solvents Triaryl and Trialkylantimony(V) Bis(catecholates) Based on 1,1' Spirobis[3,3 Dimethylindanequinone 5,6]: Abstract-A series of new binuclear bis(catecholate) antimony(V) complexes based on 1,1' spirobis[3,3 dimethylindanequinone 5,6] with various substituents at the central antimony atoms, R 3 Sb(Cat Spiro Cat)SbR 3 (I-IV) and R 3 Sb(Cat Br Spiro Br Cat)SbR 3 (V-VIII) (R = p fluorophenyl, phenyl, p tolyl, and ethyl), were synthesized. Spirobis(catecholates) I-III exhibit two one electron oxidation waves on the cycli...

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Novel neutral antimony(V) complexes were isolated as crystalline materials and characterized by IR and NMR spectroscopy: o-amidophenolate complexes [4,6-di-tert-butyl-N-(2,6-dimethylphenyl)-o-amidophenolato]triphenylantimony(V) (Ph3Sb[AP-Me], 1) and [4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-amidophenolato]triphenylantimony(v) (Ph3Sb[AP-iPr], 2); catecholate complexes (3,6-di-tert-butyl-4-methoxycatecholato)triphenylantimony(V) (Ph3Sb[(MeO)Cat], 3), its methanol solvate 3CH3OH (4); (3,6-di-tert-butyl-4,5-di-methoxycatecholato)triphenylantimony(V) (Ph3Sb[(MeO)2Cat], 5) and its acetonitrile solvate 5CH3CN (6). Complexes 1-7 were synthesized by oxidative addition of the corresponding o-iminobenzoquinones or o-benzoquinones to Ph3Sb. In the case of the phenanthrene-9,10-diolate (PhenCat) ligand, two different complexes were isolated: Ph3Sb[PhenCat] (7) and [Ph4Sb]+[Ph2Sb(PhenCat)2]- (8). Complexes 7 and 8 were found to be in equilibrium in solution. Molecular structures of 2, 4, 6, and 8 were determined by X-ray crystallography. Complexes 1-7 reversibly bind molecular oxygen to yield Ph3Sb[L-Me]O2 (9), Ph3Sb[L-iPr]O2 (10), Ph3Sb[(MeO)L']O2 (11), Ph3Sb[(MeO)2L']O2 (12) and Ph3Sb[PhenL']O2 (13), which contain five-membered trioxastibolane species (where L is the O,O',N-coordinated derivative of a 1-hydroperoxy-6-(N-aryl)-iminocyclohexa-2,4-dienol, and L' the O,O',O''-coordinated derivative of 6-hydroperoxy-6-hydroxycyclohexa-2,4-dienone). Complexes 9-13 were characterized by IR and 1H NMR spectroscopy and X-ray crystallography.

Dioxygen binds reversibly to the non‐transition‐metal complex 1 to form the spiroendoperoxide 2 (see scheme). Complexes 1 and 2 were characterized by NMR, IR, and UV/Vis spectroscopies, and their molecular structures were determined by X‐ray crystallography.

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