SYNTHESIS AND CRYSTAL-STRUCTURE OF [(ME4C2CP2SMCL.MGCL2.3THF)THF]2

[(Me4C2Cp2SmCl.MgCl2.3THF)THF]2 was prepared by the reaction of Me4C2Cp2MgCl2.4THF (Cp=C5H4, THF = tetrahydrofuran) with SmCl3 in THF. The crystals belong to triclinic space group P-1 with a 12.149(3), b 13.187(4), c 13.810(5) angstrom, alpha 117.23(2), beta 94.07(2), gamma 62.86(2)-degrees, V = 1723.9(1.0) angstrom3. In the molecular structure of the title compound there is a symmetrical centre and a quadrilateral formed by SM, Mg, Cl1, Cl2 atoms. Two centroids of the cyclopentadienyls, bridged by a tetramethylethano group form with three bridging chlorine atoms (Cl1, Cl2, Cl1a) a pseudo-trigonal bipyramid around Sm. Three oxygen atoms of THF and three chlorine atoMS (Cl1, Cl2, Cl3) constitute a distorted octahedron around Mg.

Double cyclometalation via carbon-silicon bond cleavage by palladium(II) acetate. X-ray structure of a cationic 1,4-dipalladated benzene ring and selective synthesis of heterobimetallic 1,4-phenylene-bridged platinum(II)-palladium(II) complexes

The disilylated compound 1,4-bis(trimethylsilyl)-2,3,5,6-tetrakis((dimethylamino)methyl)benzene, (Me(3)Si)(2)C2N4, 4, can be electrophilically palladated selectively at the C-Si bonds to afford the neutral 1,4-bis(palladium) complex [(AcOPd)(2)(C2N4)], from which the dicationic [(LPd)(2)(C2N4)](2+) (L = MeCN) organometallic species are accessible. The monosilylated species (Me(3)Si)(H)C2N4, 5, can be used for the preparation of the dicationic heterodinuclear platinum(II)-palladium(II) species [(LPd)(LPt)(C2N4)](2+) (L = MeCN) via a sequence of transmetalation of the organolithium derivative of 5 with [PtCl2(SEt(2))(2)], followed by a C-Si bond palladation reaction.

THE SYNTHESIS OF BRIDGED-RING CARBOCYCLES AND HETEROCYCLES VIA PALLADIUM CATALYZED REGIOSPECIFIC CYCLIZATION REACTIONS

A catalyst system comprising 10 mol % (Pd(OAc) and 20 mol % PPh3 effects the cyclisation of aryl halides onto proximate alkenes via 5-, 6-, and 7-exo-trig, and 7-endo-trig processes giving a variety of bridged-ring carbo- and hetero-cycles in excellent yield. Double bond isomerisation in the product is rarely encountered and may be suppressed by the addition of Tl(1) salts. One example of diastereospecific bis-cyclisation is given and the crystal structure of 1-aza-2-sulphonyl-3,4-benzobicyclo[3.2.1]nona-6-ene is reported.

Highly regio-, chemo- and diastereoselective synthesis of oxa-bridged spirocycles: A novel observation of reverse selectivity

The reverse regio- and diastereoselectivities are observed between the reactions involving 5- and 6-membered-ring cyclic carbonyl ylide dipoles with alpha-methylene ketones. A mild catalytic route to synthesize spirocyclic systems with high regio-, chemo- and diastereoselectivities is described.

A facile regioselective construction of spiro epoxy-bridged tetrahydropyranone frameworks

Investigations on the reactivity profile of the transient five-membered-ring cyclic carbonyl ylides, generated from alpha-diazo ketones, in the presence of the C=O group of various simple ketones and symrnetrical/unsymmetrical 1,2-diones were carried out. The reaction of alpha-diazo ketones with 1,2-naphthoquinone furnished interesting diastereomeric cycloadducts in which both the C=O groups acted as dipolarophilic sites. The similar reaction in the presence of several isatin derivatives afforded novel spiro dioxa-bridged indole derivatives as a mixture of diastereomers. The single crystal X-ray structure analysis manifestly revealed the mode of cycloaddition and the stereochemistry of two of the diastereomers. A diverse set of novel spiro epoxy-bridged tetrahydropyranone frameworks have been constructed in good yield via the tandem cyclization-cycloaddition of alpha-diazo ketones with the C=O group as heterodipolarophile in a regioselective manner. (C) 2003 Elsevier Ltd. All rights reserved.

Bromenium-Catalysed Tandem Ring Opening/Cyclisation of Vinylcyclopropanes and Vinylcyclobutanes: A Metal-Free 3+2+1]/4+2+1] Cascade for the Synthesis of Chiral Amidines and Computational Investigation

We present a detailed study of a 3+2+1] cascade cyclisation of vinylcyclopropanes (VCP) catalysed by a bromenium species (Brd+?Xd-) generated in situ, which results in the synthesis of chiral bicyclic amidines in a tandem one-pot operation. The formation of amidines involves the ring-opening of VCPs with Br?X, followed by a Ritter-type reaction with chloramine-T and a tandem cyclisation. The reaction has been further extended to vinylcyclobutane systems and involves a 4+2+1] cascade cyclisation with the same reagents. The versatility of the methodology has been demonstrated by careful choice of VCPs and VCBs to yield bicyclo4.3.0]-, -4.3.1]- and -4.4.0]amidines in enantiomerically pure form. On the basis of the experimental observations and DFT calculations, a reasonable mechanism has been put forth to account for the formation of the products and the observed stereoselectivity. We propose the existence of a p-stabilised homoallylic carbocation at the cyclopropane carbon as the reason for high stereoselectivity. DFT studies at B3LYP/6-311+G** and M06-2X/6-31+G* levels of theory in gas-phase calculations suggest the ring-opening of VCP is initiated at the p-complex stage (between the double bond and Br?X). This can be clearly perceived from the solution-phase (acetonitrile) calculations using the polarisable continuum model (PCM) solvation model, from which the extent of the ring opening of VCP was found to be noticeably high. Studies also show that the formation of zero-bridge bicyclic amidines is favoured over other bridged bicyclic amidines. The energetics of competing reaction pathways is compared to explain the product selectivity.

Mechanistic Aspects for the Formation of Copper Dimer Bridged by Phosphonic Acid and Extending Its Dimensionality by Organic and Inorganic Linkers: Synthesis, Structural Characterization, Magnetic Properties, and Theoretical Studies

Six new copper metal complexes with formulas Cu(H2O)(2,2'-bpy) (H2L)](2) center dot H4L center dot 4 H2O (1), {Cu(H2O)(2,2'-bpy)-(H3L)}(2)(H2L)]center dot 2H(2)O (2), Cu(H2O)(1,10-phen)(H2L)](2)center dot 6H(2)O (3), Cu(2,2'-bpy)(H2L)](n)center dot nH(2)O (4), Cu(1,10-phen)(H2L)](n)center dot 3nH(2)O (5), and {Cu(2,2'-bpy)(MoO3)}(2)(L)](n)center dot 2nH(2)O (6) have been synthesized starting from p-xylylenediphosphonic acid (H4L) and 2,2'-bipyridine (2,2'-bpy) or 1,10-phenanthroline (1,10-phen) as secondary linkers and characterized by single crystal X-ray diffraction analysis, IR spectroscopy, and thermogravimetric (TG) analysis. All the complexes were synthesized by hydrothermal methods. A dinuclear motif (Cu-dimer) bridged by phosphonic acid represents a new class of simple building unit (SBU) in the construction of coordination architectures in metal phosphonate chemistry. The initial pH of the reaction mixture induced by the secondary linker plays an important role in the formation of the molecular phosphonates 1, 2, and 3. Temperature dependent hydrothermal synthesis of the compounds 1, 2, and 3 reveals the mechanism of the self assembly of the compounds based on the solubility of the phosphonic acid H4L. Two-dimensional coordination polymers 4, 5, and 6, which are formed by increasing the pH of the reaction mixture, comprise Cu-dimers as nodes, organic (H2L) and inorganic (Mo4O12) ligands as linkers. The void space-areas, created by the (4,4) connected nets in compounds 4 and 5, are occupied by lattice water molecules. Thus compounds 4 and 5 have the potential to accommodate guest species/molecules. Variable temperature magnetic studies of the compounds 3, 4, 5, and 6 reveal the antiferromagnetic interactions between the two Cu(II) ions in the eight membered ring, observed in their crystal structures. A density functional theory (DFT) calculation correlates the conformation of the Cu-dimer ring with the magnitude of the exchange parameter based on the torsion angle of the conformation.

An Unusual Ring-Contraction/Rearrangement Sequence for Making Functionalized Di- and Triquinanes

A novel ring contraction/rearrangement sequence leading to functionalized 2,8-oxymethano-bridged di- and triquinane compounds is observed in the reaction of various substituted 1-methyl-4-isopropenyl-6-oxabicylo3.2.1]octan-8-ones with Lewis acids. The reaction is novel and is unprecedented for the synthesis of di- and triquinane frameworks.

An Unusual Ring-Contraction/Rearrangement Sequence for Making Functionalized Di- and Triquinanes

A novel ring contraction/rearrangement sequence leading to functionalized 2,8-oxymethano-bridged di- and triquinane compounds is observed in the reaction of various substituted 1-methyl-4-isopropenyl-6-oxabicylo3.2.1]octan-8-ones with Lewis acids. The reaction is novel and is unprecedented for the synthesis of di- and triquinane frameworks.

An Unusual Ring-Contraction/Rearrangement Sequence for Making Functionalized Di- and Triquinanes

A novel ring contraction/rearrangement sequence leading to functionalized 2,8-oxymethano-bridged di- and triquinane compounds is observed in the reaction of various substituted 1-methyl-4-isopropenyl-6-oxabicylo3.2.1]octan-8-ones with Lewis acids. The reaction is novel and is unprecedented for the synthesis of di- and triquinane frameworks.

Synthesis and characterization of (C5H9C9H6)(2)Yb(THF)(2)(II) (1) and [(C5H9C5H4)(2)Yb(THF)](2)O-2 (2), and ring-opening polymerization of lactones with 1

Reaction of YbI2 with two equivalents of cyclopentylindenyl lithium (C5H9C9H6Li) affords ytterbium(II) substituted indenyl complex (C5H9C9H6)(2)Yb(THF)(2) (1) which shows high activity to ring-opening polymerization (ROP) of lactones. The reaction between YbI2 and cyclopentylcyclopentadienyl sodium (C5H9C5H4Na) gives complex [(C5H9C5H4)(2)Yb(THF)](2)O-2 (2) in the presence of a trace amount of O-2, the molecular structure of which comprises two (C5H9C5H4)(2)Yb(THF) bridged by an asymmetric O-2 unit. The O-2 unit and ytterbium atoms define a plane that contains a C-i symmetry center.

H-1 nmr study on the ring opening selectivity of aromatic dianhydrides towards methanol

Several isomeric aromatic diester-diacids may appear as a result of the opening selectivity of anhydride groups towards the alcohol. H-1 n.m.r. was thus used to characterize the isomeric structure and to quantify the isomer composition. It was found that the isomer ratios quantitatively correlate with electron affinity of bridged dianhydrides and is independent of the alcohol structure used. Furthermore, the H-1 n.m.r chemical shift of bridged diester-diacids was found to be a very sensitive probe of chemical nature of bridged groups and can be used as indices of the opening selectivity. (C) 1997 Elsevier Science Ltd.

Ring-opening polymerisation of silver-diphosphine [M2L3] coordination cages to give [M2L3](infinity) coordination polymers

[M2L3] coordination cages and linear [M2L3]infinity polymers of the rigid, bridging diphosphines bis(diphenylphosphino)acetylene (dppa) and trans-1,2-bis(diphenylphosphino)ethylene (dppet) with silver(I) salts have been investigated in the solution and solid states. Unlike flexible diphosphines, 1:1 dppa/AgX mixtures do not selectively form discrete [Ag2(diphos)2(X)2] macrocycles; instead dynamic mixtures of one-, two- and three-coordinate complexes are formed. However, 3:2 dppa/AgX ratios (X = SbF6. BF4, O3SCF3 or NO3) do lead selectively to new [M2L3] triply bridged cage complexes [Ag2(dppa)3(X)2] 1a-d (X = SbF6 a, BF4 b, O3SCF3 c, NO3 d), which do not exhibit Ag-P bond dissociation at room temperature on the NMR time scale (121 MHz). Complexes la-d were characterised by X-ray crystallography and were found to have small internal cavities, helical conformations and multiple intramolecular aromatic interactions. The nucleophilicity of the anion subtly influences the cage shape: Increasing nucleophilicity from SbF6 (1a) through BF4 (1b) and O3SCF3 (1c) to NO3 (1d) increases the pyramidal distortion at the AgP3 centres, stretching the cage framework (with Ag...Ag distances increasing from 5.48 in 1a to 6.21 A in 1d) and giving thinner internal cavities. Crystal packing strongly affected the size of the helical twist angle, and no correlation between this parameter and the Ag-Ag distance was observed. When crystalline 1c was stored in its supernatant for 16 weeks, conversion occured to the isostoichiometric [M2L3]infinity coordination polymer [Ag(dppa)2Ag(dppa)(O3SCF3)2]infinity (1c'). X-ray crystallography revealed a structure with ten-membered Ag2(dppa)2 rings linked into infinite one-dimensional chains by a third dppa unit. The clear structural relationship between this polymer and the precursor cage 1c suggests a novel example of ring-opening polymerisation. With dppet, evidence for discrete [M2L3] cages was also found in solution, although 31P NMR spectroscopy suggested some Ag-P bond dissociation. On crystallisation, only the corresponding ring-opened polymeric structures [M2L3]infinity could be obtained. This may be because the greater steric bulk of dppet versus dppa destabilises the cage and favours the ring-opening polymerisation.

Raman spectroscopic studies of the cure of dicyclopentadiene (DCPD)

The cure of polydicyclopentadiene conducted by ring-opening metathesis polymerisation in the presence of a Grubbs catalyst was studied using non-invasive Raman spectroscopy. The spectra of the monomer precursor and polymerised product were fully characterised and all stages of polymerisation monitored. Because of the monomer's high reactivity, the cure process is adaptable to reaction injection moulding and reactive rotational moulding. The viscosity of the dicyclopentadiene undergoes a rapid change at the beginning of the polymerisation process and it is critical that the induction time of the viscosity increase is determined and controlled for successful manufacturing. The results from this work show non-invasive Raman spectroscopic monitoring to be an effective method for monitoring the degree of cure, paving the way for possible implementation of the technique as a method of real-time analysis for control and optimisation during reactive processing. Agreement is shown between Raman measurements and ultrasonic time of flight data acquired during the initial induction period of the curing process. (c) 2004 Elsevier B.V. All rights reserved.