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]

New gold(I) and silver(I) complexes with organophosphorus ligands with SPNSO skeleton. Crystal and molecular structures of monomeric [Au{(SPPh2)(O2SR)N}(PPh3)] (R = Me, C6H4Me-4) and dimeric [Ag{(SPPh2)(O2SPh)N}(PPh3)]2·2CH2Cl2

The reaction between gold(I) and silver(I) starting materials with anionic organophosphorus ligands of type [(SPPh2)(O2SR)N]- resulted in new group 11 complexes of the type [Au{(SPPh2)(O2SR)N}(tht)] (tht = tetrahydrothiophene), [Au{(SPPh2)(O2SR)N}(PPh3)], PPN[Au{(SPPh2)(O2SR)N}2] [PPN = bis(triphenylphosphine)iminium], [Ag{(SPPh2)(O2SR)N}] and [Ag{(SPPh2)(O2SR)N}(PPh3)] (R = Me, Ph, C6H4CH3-4). The new derivatives were structurally characterized by 1H and 31P NMR spectroscopy, as well as infrared and mass spectrometry. Single-crystal X-ray diffraction studies revealed monomeric structures for the gold(I) species [Au{(SPPh2)(O2SMe)N}(PPh3)] (4) and [Au{(SPPh2)(O2SC6H4Me-4)N}(PPh3)] (6), while a dimeric association was found for the silver(I) compound [Ag{(SPPh2)(O2SPh)N}(PPh3)]2·2CH2Cl2 (14·2CH2Cl2). The organophosphorus(V) ligand units have different coordination patterns, i.e. S-monometallic monoconnective in 4, S,O-monometallic biconnective in 6 and S,S,O-bimetallic triconnective in 14, respectively. © 2009 Elsevier B.V. All rights reserved.Financial support from the Ministry of Education and Research of Romania (CNCSIS, Research Project No. 1456/2007-2008) is greatly appreciated. A.P. is grateful for a research fellowship awarded by the ‘‘Babes-Bolyai” University, Cluj-Napoca, Romania.Peer Reviewe

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

C–H Bond Activation at Antimony(III): Synthesis and Reactivity of Sb(III)-Oxyaryl Species

International audienceWe report on the synthesis, structure and reactivity of [{NCNMe4}Sb(C6H2-tBu2-3,5-O-4)] (3), an organoantimony(III)-oxyaryl species obtained upon Csp2-H bond activation in a phenolate ligand and stabilised by the monoanionic pincer {NCNMe4}-. The mechanism leading to the formation of 3 is highly sensitive to steric considerations. It was probed experimentally and by DFT calculations, and a number of intermediates and related complexes were identified. All data agree with successive heterolytic bond cleaving and bond forming processes involving charged species, rather than a pathway involving free radicals as previously exemplified with congeneric bismuth species. The nucleophilic behaviour of the oxyaryl ligand in 3, a complex that features both zwitterionic and quinoidal attributes, was illustrated in derivatisation reactions. In particular, insertion of CS2 in the Sb-Coxyaryl bond generates [{NCNMe4}Sb(S2C-C6H2-tBu2-3,5-O-4)]