title: Diorganodiselenides and zinc(II) organoselenolates containing (imino)aryl groups of type 2-(RN=CH)C6H4.
abstract: Several new diorganodiselenides containing (imino)aryl groups, [2-(RN[double bond, length as m-dash]CH)C(6)H(4)](2)Se(2) [R = Me(2)NCH(2)CH(2) (4), O(CH(2)CH(2))(2)NCH(2)CH(2) (5), PhCH(2) (6), 2',6'-(i)Pr(2)C(6)H(3) (7)] were obtained by reacting [2-{(O)CH}C(6)H(4)](2)Se(2) (3) with RNH(2). Treatment of the diselenides 6 and 7 with stoichiometric amounts of K-selectride or Na resulted in isolation of the selenolates K[SeC(6)H(4)(CH[double bond, length as m-dash]NCH(2)Ph)-2] (9) and Na[SeC(6)H(4)(CH[double bond, length as m-dash]NC(6)H(3)(i)Pr(2)-2',6')-2] (10), respectively. The reaction of potassium selenolates with anhydrous ZnCl(2) (2:1 molar ratio) gave Zn[SeC(6)H(4)(CH=NCH(2)Ph)-2](2) (11) and Zn[SeC(6)H(4)(CH[double bond, length as m-dash]NC(6)H(3)(i)Pr(2)-2',6')-2](2) (12). When the dark green solution obtained from diselenide 7 and an excess of Na (after removal of the unreacted metal) was reacted with anhydrous ZnCl(2) a carbon-carbon coupling reaction occurred and the 9,10-(2',6'-(i)Pr(2)C(6)H(3)NH)(2)C(14)H(10) (8) species was obtained. The compounds were investigated in solution by multinuclear NMR ((1)H, (13)C, (77)Se, including 2D and variable temperature experiments) and by mass spectrometry. The molecular structures of 6, 8, 11 and 12 were established by single-crystal X-ray diffraction. All compounds are monomeric in the solid state. In the diselenide 6 the (imino)aryl group acts as a (C,N)-ligand resulting in a distorted T-shaped coordination geometry of type (C,N)SeX (X = Se). For the zinc complexes 11 and 12 the (Se,N) chelate pattern of the selenolato ligands results in tetrahedral Zn(Se,N)(2) cores.
authors.affiliation: Departamentul de Chimie Anorganica, Facultatea de Chimie si Inginerie Chimica, Universitatea Babes-Bolyai, RO-400028 Cluj-Napoca, Romania.
authors.forename: Alpar
authors.initials: A
authors.lastname: Pöllnitz
authors.forename: Cristian
authors.initials: C
authors.lastname: Silvestru
authors.forename: Jean-François
authors.initials: JF
authors.lastname: Carpentier
authors.forename: Anca
authors.initials: A
authors.lastname: Silvestru
mesh_terms: D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D016566:Organoselenium Compounds / Q000737:chemistry*; D012545:Schiff Bases / Q000737:chemistry; D014961:X-Ray Diffraction; D015032:Zinc / Q000737:chemistry*
chemical_list: D008024:Ligands; D016566:Organoselenium Compounds; D012545:Schiff Bases; D015032:Zinc