A Hemilabile NHC-Gold Complex and its Application to the Redox Neutral 1,2-Oxyarylation of Feedstock Alkenes.

We describe a Au complex of a hemi-labile (C^N) N-heterocyclic carbene ligand that is able to mediate oxidative addition of aryl iodides. Detailed computational and experimental investigations have been undertaken to verify and rationalize the oxidative addition process. Application of this initiation mode has resulted in the first examples of "exogenous oxidant-free" Au /Au catalyzed 1,2-oxyarylations of ethylene and propylene.

Migratory Insertion of CO into a Au-C Bond.

A MeDalPhos-ligated gold(III) metallafluorene complex, generated via C-C oxidative addition of biphenylene, reacts with CO to produce 9-fluorenone. Experimental and computational studies show that this proceeds via a hitherto unknown migratory insertion of CO into a Au(III)-C bond. This process is more energetically challenging compared to other M-C bonds, but once achieved, the product is comparatively stable with respect to retro-carbonylation.

A Systematic Study of the Effects of Complex Structure on Aryl Iodide Oxidative Addition at Bipyridyl-Ligated Gold(I) Centers.

A combined theoretical and experimental approach has been used to study the unusual mechanism of oxidative addition of aryl iodides to [bipyAu(C H )] complexes. The modular nature of this system allowed a systematic assessment of the effects of complex structure. Computational comparisons between cationic gold and the isolobal (neutral) Pd and Pt complexes revealed similar mechanistic features, but with oxidative addition being significantly favored for the group 10 metals.

Oxidative Addition of Alkenyl and Alkynyl Iodides to a Au Complex.

The first isolated examples of intermolecular oxidative addition of alkenyl and alkynyl iodides to Au are reported. Using a 5,5'-difluoro-2,2'-bipyridyl ligated complex, oxidative addition of geometrically defined alkenyl iodides occurs readily, reversibly and stereospecifically to give alkenyl-Au complexes. Conversely, reversible alkynyl iodide oxidative addition generates bimetallic complexes containing both Au and Au centers.

Hydrofunctionalisation of an Aromatic Triphosphabenzene.

The aromatic heterocycle 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene reacts with a series of silanes, germanes and stannanes, with weaker E-H bonds reacting in an increasingly facile manner. All react by 1,4-addition to give bicyclic products with diastereomeric ratios varying with the substrate. Density functional theory (DFT) calculations show that activation of the E-H bond occurs across the 1,4-C/P axis of the triphosphabenzene, with the small energetic differences with respect to the stereochemistry of the addition offering insight into the experimentally observed diastereomeric ratios.

Oxidative Addition, Transmetalation, and Reductive Elimination at a 2,2'-Bipyridyl-Ligated Gold Center.

Three-coordinate bipyridyl complexes of gold, [(κ-bipy)Au(η-CH)][NTf], are readily accessed by direct reaction of 2,2'-bipyridine (bipy), or its derivatives, with the homoleptic gold ethylene complex [Au(CH)][NTf]. The cheap and readily available bipyridyl ligands facilitate oxidative addition of aryl iodides to the Au(I) center to give [(κ-bipy)Au(Ar)I][NTf], which undergo first aryl-zinc transmetalation and second C-C reductive elimination to produce biaryl products. The products of each distinct step have been characterized.

A Transient Vinylphosphinidene via a Phosphirene-Phosphinidene Rearrangement.

A room-temperature-stable crystalline 2H-phosphirene (1) was prepared by treatment of an electrophilic diamidocarbene with tert-butylphosphaalkyne. Compound 1 is shown to react as a vinylphosphinidene generated via phosphirene-phosphinidene rearrangement. Thermolysis is shown to affect C-N bond scission while reactions with CClO or (tht)AuCl afford formal oxidation of the phosphindene center and the phosphinidene-insertion into an aromatic C-C bond of a mesityl group, respectively.

Oxidative 1,2-Difunctionalization of Ethylene via Gold-Catalyzed Oxyarylation.

Under the conditions of oxidative gold catalysis, exposure of ethylene to aryl silanes and alcohols generates products of 1,2-oxyarylation. This provides a rare example of a process that allows catalytic differential 1,2-difunctionalization of this feedstock chemical.

Computation provides chemical insight into the diverse hydride NMR chemical shifts of [Ru(NHC)(L)H] species (NHC = N-heterocyclic carbene; L = vacant, H, N, CO, MeCN, O, P, SO, H, F and Cl) and their [Ru(RPCHCHPR)(L)H] congeners.

Relativistic density functional theory calculations, both with and without the effects of spin-orbit coupling, have been employed to model hydride NMR chemical shifts for a series of [Ru(NHC)(L)H] species (NHC = N-heterocyclic carbene; L = vacant, H, N, CO, MeCN, O, P, SO, H, F and Cl), as well as selected phosphine analogues [Ru(RPCHCHPR)(L)H] (R = Pr, Cy; L = vacant, O). Inclusion of spin-orbit coupling provides good agreement with the experimental data. For the NHC systems large variations in hydride chemical shift are shown to arise from the paramagnetic term, with high net shielding (L = vacant, Cl, F) being reinforced by the contribution from spin-orbit coupling.

Au-Catalyzed Biaryl Coupling To Generate 5- to 9-Membered Rings: Turnover-Limiting Reductive Elimination versus π-Complexation.

The intramolecular gold-catalyzed arylation of arenes by aryl-trimethylsilanes has been investigated from both mechanistic and preparative aspects. The reaction generates 5- to 9-membered rings, and of the 44 examples studied, 10 include a heteroatom (N, O). Tethering of the arene to the arylsilane provides not only a tool to probe the impact of the conformational flexibility of Ar-Au-Ar intermediates, via systematic modulation of the length of aryl-aryl linkage, but also the ability to arylate neutral and electron-poor arenes-substrates that do not react at all in the intermolecular process.

Hydroboration of Phosphaalkynes by HB(C6 F5 )2.

The hydroboration of phosphaalkynes with Piers' borane (HB(C6 F5 )2 ) generated unusual phosphaalkenylboranes [RCH=PB(C6 F5 )2 ]2 that persisted as dimers in both solution and the solid state. These P2 B2 heterocycles underwent ring opening when subjected to nucleophiles, such as pyridine and tert-butylisocyanide, to yield monomeric phosphaalkenylborane adducts RCH=PB(C6 F5 )2 (L). DFT calculations were performed to probe the nature of the interaction of phosphaalkynes with boranes.

Probing the Structure, Dynamics, and Bonding of Coinage Metal Complexes of White Phosphorus.

A series of cationic white phosphorus complexes of the coinage metals Au and Cu have been synthesised and characterised both in the solid state and in solution. All complexes feature a P4 unit coordinated through an edge P-P vector (η(2)-like), although the degree of activation (as measured by the coordinated P-P bond length) is greater in the gold species. All of the cations are fluxional on the NMR timescale at room temperature, but in the case of the gold systems fluxionality is frozen out at -90 °C.

Evidence for a SN2-type pathway in the exchange of phosphines at a [PhSe]+ centre.

A range of thio- and seleno-phosphonium cationic complexes [RE(PR'3)](+)[X](-) (R = Me, Ph; E = S, Se; X = GaCl4, SbF6) have been synthesised and structurally characterised. Reaction of [PhSPPh3][GaCl4] and [PhSePPh3][GaCl4] with P(t)Bu3 results in the ready transfer of the "RS(+)" and "RSe(+)" fragments from PPh3 to the stronger electron donor P(t)Bu3. NMR experiments combined with an Eyring analysis on the corresponding degenerate phosphine exchange reaction allowed the thermodynamic values for the phosphine exchange reaction of the sulfur cation (ΔH(‡) 18.

Hydrogen activation by an aromatic triphosphabenzene.

Aromatic hydrogenation is a challenging transformation typically requiring alkali or transition metal reagents and/or harsh conditions to facilitate the process. In sharp contrast, the aromatic heterocycle 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene is shown to be reduced under 4 atm of H2 to give [3.1.

Gold-catalyzed oxidative coupling of arylsilanes and arenes: origin of selectivity and improved precatalyst.

The mechanism of gold-catalyzed coupling of arenes with aryltrimethylsilanes has been investigated, employing an improved precatalyst (thtAuBr3) to facilitate kinetic analysis. In combination with linear free-energy relationships, kinetic isotope effects, and stoichiometric experiments, the data support a mechanism involving an Au(I)/Au(III) redox cycle in which sequential electrophilic aromatic substitution of the arylsilane and the arene by Au(III) precedes product-forming reductive elimination and subsequent cycle-closing reoxidation of the metal. Despite the fundamental mechanistic similarities between the two auration events, high selectivity is observed for heterocoupling (C-Si then C-H auration) over homocoupling of either the arylsilane or the arene (C-Si then C-Si, or C-H then C-H auration); this chemoselectivity originates from differences in the product-determining elementary steps of each electrophilic substitution.

A polycyclic borazine radical cation: [1,2-B2{1,2-(MeN)2C6H4}2]˙(+).

The radical cation [1,2-B2{1,2-(MeN)2C6H4}2]˙(+) has been synthesised and its structure and bonding have been probed using a combination of X-ray crystallography, EPR spectroscopy and DFT calculations which show that it represents a new type of radical centred primarily on two N-heterocyclic units joined by a B2 linker but with only a minor contribution from boron-based orbitals.

Coordination chemistry of trimethylsilylphosphaalkyne: a phosphaalkyne bearing a reactive substituent.

Trimethylsilylphosphaalkyne binds readily to a variety of transition metals. Binding can take place using either the end-on or side-on mode and to either mononuclear or multinuclear metal complexes. The synthesis, structure and characterisation of eight such complexes, [Cp(2)Zr(PMe(3))(Me(3)SiC≡P)], [(C(6)F(5))(2)FB(C(6)F(4))PCSiMe(3))ZrCp(2)(PMe(3))], [(C(6)F(5))(2)XB(C(6)F(4))(ZrCp(2))(2)P(2)(CSiMe(3))(2)] (X = F/H), [(Me(3)Si-C≡P)(2)Mo(dppe)(2)], [CpMo(CO)(2)PC(SiMe(3))Mo(CO)(2)Cp], [(Ph(3)P)(2)Pt(Me(3)SiC≡P)], [{(dppe)Pd}(2)(Me(3)SiC≡P)] and [Pd(5)(PPh(3))(5)(Me(3)SiC≡P)(3)] are described together with attempts to desilylate some of these complexes.

Gold-catalyzed direct arylation.

Biaryls (two directly connected aromatic rings, Ar(1)-Ar(2)) are common motifs in pharmaceuticals, agrochemicals, and organic materials. Current methods for establishing the Ar(1)-Ar(2) bond are dominated by the cross-coupling of aryl halides (Ar(1)-X) with aryl metallics (Ar(2)-M). We report that, in the presence of 1 to 2 mole percent of a gold catalyst and a mild oxidant, a wide range of arenes (Ar(1)-H) undergo site-selective arylation by arylsilanes (Ar(2)-SiMe(3)) to generate biaryls (Ar(1)-Ar(2)), with little or no homocoupling (Ar(1)-Ar(1)/Ar(2)-Ar(2)).

Gold-catalysed oxyarylation of styrenes and mono- and gem-disubstituted olefins facilitated by an iodine(III) oxidant.

1-Hydroxy-1,2-benziodoxol-3(1H)-one (IBA) is an efficient terminal oxidant for gold-catalysed, three-component oxyarylation reactions. The use of this iodine(III) reagent expands the scope of oxyarylation to include styrenes and gem-disubstituted olefins, substrates that are incompatible with the previously reported Selectfluor-based methodology. Diverse arylsilane coupling partners can be employed, and in benzotrifluoride, homocoupling is substantially reduced.

White phosphorus as a ligand for the coinage metals.

Reaction of equimolar quantities of MX (M = Au, Cu, X = Cl; M = Ag, X = OTf) and GaCl(3) in CH(2)Cl(2) with P(4) leads to phosphorus ligating a cationic coinage metal centre. For Cu and Ag, ion-contacted coordination polymers are formed; for Au, an ion-separated complex is observed that features the [Au(η(2)-P(4))(2)](+) cation, which is the first homoleptic Au-P(4) complex to be characterised in the condensed phase.

The coordination and polymerisation of cyclic 1,3-dienes by gold(I) cations.

Cyclopentadiene and 1,3-cyclohexadiene are readily polymerised by [LAu][X]. With specific ancillary ligands polymerisation was suppressed and a molecular species involving an Au(I) cation η(2)-bonding CpH was isolated and whose structure was probed in both the solid state and in solution.

A variable-temperature study of 1,2-bis(dimethylamino)-1,2-bis(2,6-dimethylanilino)diborane.

The title compound, C(20)H(32)B(2)N(4), is monoclinic at ambient temperature but triclinic (pseudo-monoclinic) below 150 K. The structures of the two phases, determined at 200 and 120 K, respectively, are very similar, the molecular symmetry being crystallographic C(2) and approximate (local) C(2), respectively. There is significant π conjugation within each N-B-N moiety, but none between them or between the N-B-N and arene moieties.

The effects of day-to-day variability of physiological data on operator functional state classification.

The application of pattern classification techniques to physiological data has undergone rapid expansion. Tasks as varied as the diagnosis of disease from magnetic resonance images, brain-computer interfaces for the disabled, and the decoding of brain functioning based on electrical activity have been accomplished quite successfully with pattern classification. These classifiers have been further applied in complex cognitive tasks to improve performance, in one example as an input to adaptive automation.