11-(2,2-Dimethylpropyl)-12-{2-[12-(2,2-dimethylpropyl)- 9,10-dihydro-9,10-ethenoanthracen-11-yl]- ethyl}-9,10-dihydro-9,10-ethenoanthracene

Reaction of tert-butyllithium with 11,12-dimethylene-9,10- dihydro-9,10-ethanoanthracene and 4,5-diiodopentacyclo- [4.3.0.02,4.03,8.05,7]nonane gives three products, one of which crystallizes from petroleum ether as the title compound, C44H46, (I). Molecules of (I) are positioned on inversion centers (Z0 = 0.5) in the space group P21/n and lack any discernible intermolecular interactions

11-(2,2-Dimethylpropyl)-12-{2-[12-(2,2-dimethylpropyl)- 9,10-dihydro-9,10-ethenoanthracen-11-yl]- ethyl}-9,10-dihydro-9,10-ethenoanthracene

Reaction of tert-butyllithium with 11,12-dimethylene-9,10- dihydro-9,10-ethanoanthracene and 4,5-diiodopentacyclo- [4.3.0.02,4.03,8.05,7]nonane gives three products, one of which crystallizes from petroleum ether as the title compound, C44H46, (I). Molecules of (I) are positioned on inversion centers (Z0 = 0.5) in the space group P21/n and lack any discernible intermolecular interactions

Synthesis and Molecular and Extended Structures for a Diaminonaphthalene-Derived Bis(amido)stannylene

The cyclic bis(amido)tin(II) compound Sn[1,8-(iPrN)2C10H6] (2) was isolated from the reaction of Li2[1,8-(iPrN)2C10H6] (1) and SnCl2. Solid-state structural analysis of 2 showed it to be a mononuclear species with a pyramidal Sn center as part of a nonplanar metallaheterocycle. The packing diagram of 2 revealed an extended one-dimensional head-to-tail chain structure with short intermolecular Sn/arene-C interactions. Computational examination of 2 (DFT/PW91 and MP2 with 6-31G* and 6-311G** basis functions) indicated that the optimum gas-phase structure of 2, which displays a Sn center in the plane of the naphthyl backbone with a slightly twisted metallaheterocycle, is approximately 24 kcal/mol lower in energy than the X-ray structure. The solid-state geometry of 2 is attributed to the intermolecular donation of the naphthalene -electrons to a Lewis acidic Sn center, which leads to the observed supramolecular structure. The crystal structure of 1 is also reported.NRC publication: Ye

A stable silylene in a reactive environment: Synthesis, reactivity, and silicon extrusion chemistry of a coordinatively unsaturated ruthenium silylene complex containing chloride and η\u3csup\u3e3\u3c/sup\u3e-P-C-P ligands

Reaction of [(dcypb)ClRu(μ-Cl)3Ru(dcypb)(N2)] (1) with 4 equiv of the stable silylene 1,3-di-tert-butyl-l,3,2-diazasilol-2-ylidene (SiL2N) yields coordinatively unsaturated RuCl(η3-dcypb)(SiL2N) (2). Complex 2 is a rare example of a trans-spanning diphosphine complex, this geometry resulting from an unprecedented attack of the metal on the tetramethylene ligand backbone. X-ray and solid-state 31P NMR and IR analysis reveal an agostic interaction between the metal and a silylene But group. In solution, this interaction is observed only at low temperature. Reaction of 2 with H2 containing trace H2O yields siloxane dimer [L2NSi-(H)]2O 3 and the ruthenium hydride-H2 adduct [(dcypb)(H)Ru(μ-Cl)2(μ-H)Ru(dcypb)(H2)] (4). Attempts to isolate 4 resulted in serendipitous crystallization of decomposition product 5, [(dcypb)(H)Ru(μ-Cl)3Ru(dcypb)(N2)]. X-ray analysis of 5 revealed a structure closely analogous to that of 4, in which bridging hydride is replaced by chloride, and η2-H2 by η2N2. Displacement of silylene from 2 is facile: treatment with 1 atm of CO affords free SiL2N, accompanied by RuCl(η3-dcypb)(CO)2 as a mixture of three isomers (6-8)

Dinuclear copper(II) chloro complex of the ligand 2,3,5,6-tetra(2-pyridyl) pyrazine

Crystallographic and magnetic studies have been performed on the complex, [{CuCl}2(μ-tppz)][PF6]2, where tppz is 2,3,5,6-tetra-2-pyridinylpyrazine. The crystal structure revealed an infinite, ionic chain wherein Cu(II) ions are respectively above and below the plane of the pyrazine moiety of the bridging tppz ligand with the pyridine moieties moving out of the pyrazine plane in order to coordinate to Cu(II). Each chloride ligand bonds equatorially to Cu(II) in a [{CuCl}2(μ-tppz)] 2+ ion and axially to a neighboring [{CuCl}2(μ-tppz)] 2+ ion so as to form a one-dimensional chain in the solid state. The temperature-dependent magnetic susceptibilitity could be satisfactorily fitted by using a modified Bleaney-Bowers expression (for H = -JSa • Sb J = -5.6 cm-1 and g = 2.16) where the exchange interaction is suggested to involve the orbitals of the tppz ligand

Phenylcyanamidoruthenium scorpionate complexes

Nine [Ru(Tp)(dppe)L] complexes, where Tp is hydrotris(pyrazol-1-yl)borate, dppe is ethylenebis(diphenylphosphine), and L is (4-nitrophenyl)cyanamide (NO2pcyd-), (2-chlorophenyl)cyanamide (2-Clpcyd -), (3-chlorophenyl)cyanamide (3-Clpcyd-), (2,4-dichlorophenyl)cyanamide (2,4-Cl2pcyd-), (2,3-dichlorophenyl)cyanamide (2,3-Cl2pcyd-), (2,5-dichlorophenyl)cyanamide (2,5-Cl2pcyd-), (2,4,5-trichlorophenyl)cyanamide (2,4,5-Cl3pcyd-), (2,3,5,6-tetrachlorophenyl)cyanamide (2,3,5,6-Cl4pcyd-), and (pentachlorophenyl)cyanamide (Cl5pcyd-), and the dinuclear complex [{Ru(Tp)(dppe)}2(μ-adpc)], where adpc 2- is azo-4,4-diphenylcyanamide, have been prepared and characterized. The crystal structures of [Ru(Tp)(dppe)(Cl5pcyd)] and [{Ru(Tp)(dppe)}2(μ-adpc)] reveal the RuII ion to occupy a pseudooctahedral coordination sphere in which the cyanamide ligand coordinates to RuII by its terminal nitrogen atom. For both complexes, the cyanamide ligands are planar, indicating significant π mixing between the cyanamide and phenyl moieties as well as the azo group in the case of adpc2-. The optical spectra of the nominally ruthenium(III) species [Ru(Tp)(dppe)L]+ were obtained through spectroelectrochemistry measurements and showed an intense near-IR absorption band. Time-dependent density functional theory calculations of these species revealed that oxidation of the ruthenium(II) species led to species where partial oxidation of the cyanamide ligand had occurred, indicative of noninnocent character for these ligands. The spin densities reveal that while the 3-Clpycd species h

Two new end-to-end single dicyanamide bridged Cu(II) complexes with Schiff base ligands: Structural, electrochemical and magnetic properties

International audienceThe synthesis, crystal structures and magnetic properties of two different copper(II) complexes of formula [Cu(L1)(dca)]n · nClO4 (1) and [Cu(L2)]2(dca)(ClO4) (2) [L1 = N,N-dimethylethylene-N′-(pyridine-2-carbaldiiminato), HL2 = N,N-dimethylethylene-N′-salicylaldiiminato, dca = dicyanamide anion] are described. Spectroscopic and electrochemical properties have also been discussed. A one-dimensional chain structure with single, symmetrical, μ1,5-dca bridges is found in compound 1. The copper atom in 1 has a square pyramidal geometry. A tridentate Schiff base ligand, having NNN donor sites, and one nitrogen atom from dca occupy the basal plane. N(18) of a neighbouring unit occupies the apical site. The Schiff base used in compound 2 is a tridentate anion with NNO donor sites, which changes the structure in a dinuclear unit of copper atoms bridged by single end-to-end dicyanamide ion. The environment around copper in 2 is square planar. Magnetic susceptibility measurements for 1 and 2 reveal the occurrence of weak antiferromagnetic interaction through the dca ligand

Heteroleptic iminopyrrolidinates of aluminium

A series of iminopyrrolidine (ip) compounds were synthesized with excellent yields as potential ligands for novel organometallic precursors for atomic layer deposition. The idea behind these ligands was that carbodiimide (CDI) deinsertion would not occur as the quaternary carbon was tethered to one chelate nitrogen. To our advantage a melting point trend was evident within the ip ligands and reflected in the family of heteroleptic aluminium species when the ip ligands were reacted with TMA or TEA. The alkane elimination reaction occurred at room temperature yielding clean products with high yields. Crystal structures were collected for compounds 7 [ipipAlMe2], 12 [tbipAlMe2], and 14 [sbipAlEt2] demonstrating that the heteroleptic aluminium species were dimers. This was also evident in the mass spectra collected for each compound as the parent peak was that of the dimer minus a methyl. Thermolysis studies were carried out on all the ipAlMe 2 species to observe the decomposition at an isotherm over several days. The decay of the methyl peak was monitored as a ratio against TMS within the solution and was shown to be a first order decomposition. From these studies it was clear that nbip (9), iso-bip (10), and tbip (12) were the most stable complexes with half-lives of 24.8, 9.00, and 10.3 days, respective