A new ortho­rhom­bic polymorph of 1,1′-seleno­bis­(N,N-diethyl­sulfanecarbothio­amide)

The title compound [systematic name: N,N-dieth­yl({[(diethyl­carbamothio­yl)sulfan­yl]selan­yl}sulfan­yl)carbothio­amide], C10H20N2S4Se, crystallizes in a new form in the space group Pca21: the previously reported polymorph crystallizes in the space group P212121. The new phase contains two independent mol­ecules in the asymmetric unit. The Se atoms are tetra­coordinated, with a distorted square-planar geometry. The ligands coordinate asymmetrically to the Se atoms, with one strong Se—S bond [range 2.2833 (13)–2.3041 (15) Å] and one weaker bond [range 2.7318 (14)–2.7873 (12) Å]

Organoselenium( II ) halides containing the pincer 2,6-(Me 2 NCH 2 ) 2 C 6 H 3 ligand – an experimental and theoretical investigation

New organoselenium( II )halidesofthetype[RSe] + X − [R = 2,6-(Me 2 NCH 2 ) 2 C 6 H 3 ;X=Cl( 2 ), Br ( 3 ), I ( 4 )] were prepared by cleavage of the Se – Se bond in R 2 Se 2 ( 1 )withSO 2 Cl 2 followed by halogen exchange when organo- selenium chloride was treated with NaBr or KI. The reaction between 2 and R ’ 2 MCl n resulted in new ionic [RSe] + [R ’ 2 MCl n +1 ] − [R ’ =2-(Me 2 NCH 2 )C 6 H 4 , n =1,M=Sb( 5 ), Bi ( 6 ); R ’ =Ph,M=Sb, n =1( 7 )or n =3( 8 )] species. All new compounds were investigated in solution by multinuclear NMR spectroscopy ( 1 H, 13 C, 77 Se, 2D experiments) and mass spectrometry. The ionic nature of 2 and the antimonates species was con fi rmed by conductivity studies. The molecular structures of [{2,6-(Me 2 NCH 2 ) 2 C 6 H 3 }Se] + Cl − · n H 2 O( 2 ·H 2 Oand 2 ·2H 2 O) and [{2,6-(Me 2 NCH 2 ) 2 C 6 H 3 }Se] + [Ph 2 SbCl 4 ] − ( 8 ), respectively, were established by single-crystal X-ray di ff raction, pointing out that the ionic nature of the se compounds is also preserved in the solid state, with both nitrogen atoms strongly trans coordinated to the selenium atom of the cation. Theoretical calculations carried out at the DFT level were exploite d to investigate the nature of the bonding in compounds 2 – 4 and the free cation [RSe] + ( 2a ). A topological analysis based on the theory of Atoms-In-Molecules (AIM) and Electron Localization Function (ELF) jointly to a Natural Bond Orbital (NBO) approach was used to shed light on the e ff ect of the nature of the halogen specie s X on the bonding within the 3c-4e N – Se – Nmoiet

[2,6-Bis(dimethyl­amino­meth­yl)phen­yl]selenium bromide monohydrate

In the title hydrated molecular salt, C12H19N2Se+·Br−·H2O, the two independent bromide anions lie on a twofold rotation axis. Strong intra­molecular N→Se inter­actions [2.185 (3) and 2.181 (3) Å] are established by both N atoms of the organic group in the cation, in trans positions to each other, with an N—Se—N angle of 161.6 (1)°, resulting in a T-shaped (C,N,N′)Se core. In the crystal, dimeric associations are formed by Br⋯Se [3.662 (2) Å] and Br⋯H inter­actions [2.56 (6) and 2.63 (7) Å] involving two bromide anions, two cations and two water mol­ecules

Diorganodiselenides and zinc(II) organoselenolates containing (imino)aryl groups of type 2-(RN=CH)C6H4.

International audienceSeveral 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

Group 12 metal aryl selenolates. Crystal and molecular structure of [2-(Et2NCH2)C6H4]2Se 2 and [2-(Me2NCH2)C6H 4Se]2M (M = Zn, Cd)

Diorganodiselenide [2-(Et2NCH2)C6H 4]2Se2 (1) was obtained by hydrolysis/oxidation of the corresponding [2-(Et2NCH2)C6H 4]SeLi derivative. The treatment of [2-(Et2NCH 2)C6H4]2Se2 with elemental sodium in THF resulted in [2-(Et2NCH2)C 6H4]SeNa (2). Reactions between alkali metal selenolates [2-(R2NCH2)C6H4]SeM′ (R = Me, Et; M′ = Li, Na) and MCl2 (M = Zn, Cd) in a 2:1 molar ratio resulted in the [2-(R2NCH2)C6H 4Se]2M species [R = Me, M = Zn (3), Cd (4); R = Et, M = Zn (5), Cd (6)]. The new compounds were characterized by multinuclear NMR ( 1H, 13C, 77Se, 113Cd) and mass spectrometry. The crystal and molecular structures of 1, 3 and 4 revealed monomeric species stabilized by N → Se (for 1) and N → M (for 3 and 4) intramolecular interactions. © 2010 Elsevier B.V. All rights reserved.Financial support from National University Research Council and Ministry of Education and Research of Romania (Research Projects CEx 11-55/2006 and PNII-ID 2404/2008) is greatly appreciated.Peer Reviewe

Ammonium salts of organophosphorus acids. Crystal and molecular structure of [Et3NH]+[(SPMe2)(SPPh2)N]- and [2-(O(CH2CH2)2N(H)CH2)C6H4]+[S2P(OPri)2]-

8 páginas, 4 figuras, 2 tablas, 1 esquema.The ammonium salts [Et3NH]+L- {L- = [(SPMe2)(SPPh2)N]- (1), Ph2PS2 - (2)} were obtained in the reaction between triethylamine and the corresponding organophosphorus acid in a 1:1 molar ratio, while [2-{O(CH2CH2)2N(H)CH2}C6H4]+[S2P(OPri)2]- (3) resulted as hydrolysis product in the process of growing crystals of [2-{O(CH2CH2)2N(H)CH2}C6H4SeS2P(OPri)2. Compounds 1 and 2 were characterized by 1H and 31P NMR spectroscopy. Single-crystal X-ray diffraction studies revealed the presence of short intermolecular S···H contacts which result in the formation of dimeric units in 1 and of a layered supramolecular structure in 3.This work was supported by the National University Research Council of Romania (CNCSIS, Research Project No. ID-2404/2008). A. M. P. thanks the European Social Fund for a Scholarship (Education and Training Program 2008-2013, POSDRU/6/1.5/S/3).Peer reviewe

Cu(II) and Ag(I) complexes of the pyrazole-derived diorganoselenide (pzCH2CH2)2Se. Synthesis, solid state structure and solution behavior

The diorganoselenide (pzCH2CH2)2Se (R2Se (1), pz = pyrazole) was prepared by reacting the in situ obtained Na2Se with 1-(2-bromoethyl)-1H-pyrazole in a water/ethanol mixture. Copper(II) and silver(I) complexes of type [CuX2{Se(CH2CH2pz)2}] [X = Cl (2), Br (3), NO3 (4), ClO4 (5)] and [AgX{Se(CH2CH2pz)2}] [X = OTf (6) (OTf = CF3SO3), NO3 (7), ClO4 (8)] were obtained by reacting the ligand 1 with the appropriate copper(II) and silver(I) salt in 1:1 molar ratio. The ligand and the metal complexes were investigated by appropriate spectroscopic methods, both in solution and in solid state: multinuclear NMR (1H, 13C, 19F, 77Se), UV–Vis spectroscopy, ESI mass spectrometry, IR spectroscopy and molar conductivity. The metal complexes 2, 3 and 6–8 behave as 1:1 electrolytes in solution, while 4 and 5 behave as 1:2 electrolytes. The molecular structures of complexes [CuX2{Se(CH2CH2pz)2}] [X = Cl (2), Br (3), NO3 (4)], [Cu(ClO4)2{Se(CH2CH2pz)2}(H2O)] (5⋅H2O) and [AgOTf {Se(CH2CH2pz)2}] (6) were determined by single-crystal X-ray diffraction. The (pzCH2CH2)2Se ligand acts as a N, Se,N chelating moiety in 2, 3, 4 and 5⋅H2O and as a bridging, tetraconnective 2 × N,Se unit in 6