Triphenylantimony(v) catecholates and o-amidophenolates: reversible binding of molecular oxygen.
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.
Cherkasov
Vladimir K
VK
G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinina Street, 603950 Nizhny Novgorod, Russia. cherkasov@imoc.sinn.ru
Abakumov
Gleb A
GA
Grunova
Ekaterina V
EV
Poddel'sky
Andrey I
AI
Fukin
Georgy K
GK
Baranov
Evgenii V
EV
Kurskii
Yury V
YV
Abakumova
Ludmila G
LG
D002396:Catechols / Q000737:chemistry; D002621:Chemistry / Q000379:methods*; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D010100:Oxygen / Q000378:metabolism*; D010636:Phenols / Q000737:chemistry; D011809:Quinones / Q000737:chemistry; D013055:Spectrophotometry, Infrared
D002396:Catechols; D010636:Phenols; D011809:Quinones; D010100:Oxygen