C-H bond activation at antimony(III): synthesis and reactivity of Sb(III)-oxyaryl species.

We 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)].

Triphenylbismuth(v) di[(iso)nicotinates] - transmetallation agents or divergent organometalloligands? First organobismuth(v)-based silver(i) coordination polymers.

The reaction of Ph3BiCl2 with alkali salts of isonicotinic and nicotinic acids afforded Ph3Bi[O(O)CC5H4N-4]2 (1) and Ph3Bi[O(O)CC5H4N-3]2 (2), respectively, which were characterized by multinuclear NMR spectroscopy in solution, mass spectrometry and IR spectroscopy in the solid state. Their molecular structures were established by single-crystal X-ray diffraction. For both 1 and 2 the molecules contain a trigonal bipyramidal C3BiO2 core, with the phenyl groups in equatorial positions. The potential use of 1 and 2 as ditopic organometalloligands was investigated. The reaction of 1 or 2 with Me3SnCl (1 : 2 molar ratio) resulted in carboxylato ligand exchange and the formation of Me3Sn[O(O)CC5H4N-4] (3) and Me3Sn[O(O)CC5H4N-3] (4) besides Ph3BiCl2. The crystals of both 3 and 4 contain 1-D coordination polymers built through intermolecular N → Sn interactions. The treatment of Ni[S2P(OiPr)2]2 with 1 and 2, respectively, resulted, in addition to di(carboxylato)nickel(ii) derivatives, in isolation of Ph3Bi and the disulphane [(iPrO)2P(S)S]2. New coordination polymers were obtained by reacting 1 and 2 with various silver(i) salts: [Ag{Ph3Bi[O(O)CC5H4N-4]2}(OTf)] (5), [Ag{Ph3Bi[O(O)CC5H4N-3]2}(OTf)]·CH2Cl2 (6·CH2Cl2), [Ag{Ph3Bi[O(O)CC5H4N-4]2}](SbF6)·2THF (7·2THF), [Ag{Ph3Bi[O(O)CC5H4N-3]2}](SbF6)·CH2Cl2 (8·CH2Cl2) and [Ag{Ph3Bi[O(O)CC5H4N-3]2}(NO3)]·CH2Cl2 (9·CH2Cl2). The crystal structures of 5 and 6 can be described as 1-D chains linked by triflate bridges in pairs of chains and 2-D networks, respectively. Compound 7 features a 2-D grid-like topology of the network, with tecton 1 acting as a tridentate ligand through both nitrogen and one oxygen atoms. The linker 2 molecules adopt either cis (compound 6) or trans (compounds 8 and 9) conformation. Complexes 8 and 9 are 1-D chain polymers exhibiting zig-zag and wavy motifs, respectively. The dimensionality of the structures is extended by the presence of supramolecular interactions (ππ, AgAg, AgO).

A general route to monoorganopnicogen(III) (M = Sb, Bi) compounds with a pincer (N,C,N) group and oxo ligands.

The reaction of RMCl2 [R = 2,6-[MeN(CH2CH2)2NCH2]2C6H3; M = Sb (1), Bi (2)] with KOH affords the isolation of the oxides cyclo-R2M2O2 [M = Sb (3), Bi (4)]. Treatment of 3 with trifluoroacetic acid produced an ionic species (5) with a dinuclear cation that contains organic ligands protonated partially at one of the pendant arms. The cyclic oxides 3 and 4 are able to trap gaseous CO2 to give "RMCO3" [M = Sb (6), Bi (7)], the degree of these organometallic carbonates' oligomerization being under investigation. The reactivity of the dinuclear oxide 3 was also investigated towards oxalic acid or dopamine hydrochloride and pure mononuclear compounds could be isolated, i.e. RSb[O(O)CC(O)O] (8) and RSb[O2-1,2-C6H3-3-(CH2)2NH3]Cl (9). The reaction of the dichlorides 1 and 2 with ethylene glycol, pinacol or catechol, in the presence of KOH, led to 2-organo-1,3,2-dioxastibolanes or -bismolanes RM(OCH2)2 [M = Sb (10), Bi (11)], RM(OCMe2)2 [M = Sb (12), Bi (13)] and 2-organo-1,3,2-dioxastibole or -bismole RM(O2-1,2-C6H4) [M = Sb (14), Bi (15)], respectively. The compounds were investigated by NMR spectroscopy, including variable temperature experiments, providing evidence for the presence of the intramolecular N→M interactions in solution. Single crystal X-ray diffraction studies were performed for most compounds and revealed an organic group R acting as a pincer ligand resulting in a distorted square pyramidal (N,C,N)MO2 core with cis intramolecular N→M interactions placed trans to M­O bonds. This is in contrast to the N→M interactions trans to each other as found in the RMCl2 used as starting materials. The crystals of the oxides 3 and 4·4H2O contain different geometric isomers with anti and syn orientation of the M­C bonds, respectively, with respect to the planar M2O2 ring. In the supramolecular polymeric architecture established in the crystal of 4·4H2O an important finding is the experimental observation of water hexamer units with a [tetramer + 2] structure (water molecules connected to opposite corners of a square water tetramer) fixed between 1D-chains of the type (syn-R2Bi2O2·H2O)n through additional hydrogen bonds to oxygen atoms of the dinuclear organobismuth(III) moieties. Theoretical calculations were carried out on 2­6 and 8­15 in order to gain insight into the stabilization energy produced by intramolecular coordination of the pendant arms, association degrees and formation energies of the organopnicogen compounds with chelating ligands.

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

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.

The ring-chain tautomeric equilibria of selenium macrocyclic compounds: the isolation of the ring tautomer.

A broadening of the investigation of the ring-chain tautomeric process of N-substituted 1,3-X,N-heterocycles (X = O, S, NR) to Se containing macrocyclic compounds allowed the isolation and structurally solid state characterization of the cyclic tautomer 7, which due to the length of the aliphatic chain, is able to form a stable six-membered ring (6-endo-trig). The theoretical calculations based on the DFT method (Gaussian 03 software package) also support the fact that tautomer 7 is more stable than the chain tautomer 6. Thus, based on the ring-chain tautomerism of the macrocycles that contain alkyl chains with amino-imino, imino-alcohol or sulphur-imino groups, combined with a strategy that allows the formation of a stable six-membered ring, the main reaction products will be the cyclic tautomers. The ring-chain equilibria of these macrocycles could be exploited advantageously in different areas of macrocyclic, physical and medicinal chemistry in order to obtain compounds with practical applications.

Organomercury(II) and tellurium(II) compounds with the "pincer" ligand 2,6-[O(CH2CH2)2NCH2]2C6H3--stabilization of an unusual organotellurium(II) cationic species.

The reaction of RH (1) with Hg(OAc)(2), in EtOH, gave the acetate RHgOAc (2) [R = 2,6-[O(CH(2)CH(2))(2)NCH(2)](2)C(6)H(3)]. The corresponding RHgCl (3) was obtained from 2 and LiCl. The reaction of 3 with TeCl(4) (1:1 molar ratio), in anhydrous 1,4-dioxane, resulted in the transfer of the organic ligand from mercury to tellurium and the isolation of the unexpected ionic compounds [RTe](2)[Hg(2)Cl(6)] (4) and [RH(3)][HgCl(4)] (5). The molecular structures of 1-4 and 5·H(2)O were established by single-crystal X-ray diffraction. The acetate 2 and the chloride 3 are monomeric in solid state. In both mercury and tellurium organometallic compounds the organic group acts as an (N,C,N) "pincer" ligand. This coordination pattern provided stability for the rare [RTe](+) cation. Weak cation-anion interactions [Te···Cl 3.869(3) Å] are present between [RTe](+) and the dinuclear anion [Hg(2)Cl(6)](2-) in the crystal of 4. Theoretical calculations with DFT methods were performed for models of 3 and 4. The results show that in the cation of 4 the coordination of the nitrogen atoms play an important role for the stabilization of the structure found in the crystal whereas in 3 the coordination of the nitrogen atoms to the metal centre stabilizes to a less extent the structure found in solid state.

A new ortho-rhom-bic polymorph of 1,1'-seleno-bis-(N,N-diethyl-sulfanecarbothio-amide).

THE TITLE COMPOUND [SYSTEMATIC NAME: N,N-dieth-yl({[(diethyl-carbamothio-yl)sulfan-yl]selan-yl}sulfan-yl)carbothio-amide], C(10)H(20)N(2)S(4)Se, crystallizes in a new form in the space group Pca2(1): the previously reported polymorph crystallizes in the space group P2(1)2(1)2(1). The new phase contains two independent mol-ecules in the asymmetric unit. The Se atoms are tetra-coordinated, 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].