James D E T Wilton-Ely

• PhD Organometallic Chemistry
• Lecturer at Imperial College London

Three-way catalysts (TWCs) are widely used in vehicles to convert the exhaust emissions from internal combustion engines into less toxic pollutants. After around 8–10 years of use, the declining catalytic activity of TWCs causes them to need replacing, leading to the generation of substantial amounts of spent TWC material containing precious metals...

Despite the greater awareness of elemental sustainability and the benefits of the circular economy concept, much waste electrical and electronic equipment (WEEE) is still destined for landfill. Effective methods for valorizing this waste within our society are therefore imperative. In this contribution, two gold(III) complexes obtained as recovery...

The direct use in catalysis of precious metal recovery products from industrial and consumer waste is a very promising recent area of investigation. It represents a more sustainable, environmentally benign, and profitable way of managing the low abundance of precious metals, as well as encouraging new ways of exploiting their catalytic properties....

[PdI2(Me2dazdt)] is obtained from palladium powder via a 100% atom economical Pd(0) leaching reaction using Me2dazdt (N,N’-dimethyl-perhydrodiazepine-2,3-dithione) and iodine. This complex is a versatile starting point for ligand exchange reactions with (di)phosphines, yielding trans-[PdI2(PPh3)2] and [PdI2(dppe)] (dppe = 1,2-bis(diphenylphosphino)...

A two-photon fluorescent probe based on a ruthenium(II) vinyl complex is capable of selectively detecting carbon monoxide in cells and ex vivo using mice with a subcutaneous air pouch as a model for inflammation. This probe combines highly selective and sensitive ex vivo detection of endogenous CO in a realistic model with facile, inexpensive synth...

The disulfide ligand (SC6H4CO2H-4)2 acts as a simple but versatile linker for a range of group 8 transition metals through reaction of the oxygen donors. This leads to a range of homobimetallic ruthenium and osmium alkenyl compounds, [{M(CH=CHR)(CO)(PPh3)2(O2CC6H4S-4)}2] (M = Ru, Os; R = C6H4Me-4). Additional metal-based functionality can be added...

The versatile rhenium complex [ReCl(CO)3(bpyC[triple bond, length as m-dash]CH)] (HC[triple bond, length as m-dash]Cbpy = 5-ethynyl-2,2'-bipyridine) is used to generate a series of bimetallic complexes through the hydrometallation of [MHCl(CO)(BTD)(PPh3)2] (M = Ru, Os; BTD = 2,1,3-benzothiadiazole). The ruthenium complex [Ru{CH[double bond, length...

Cellulose is the single largest component of lignocellulosic biomass and is an attractive feedstock for a wide variety of renewable platform chemicals and biofuels, providing an alternative to petrochemicals and petrofuels. This potential is currently limited by the existing methods of transforming this poorly soluble polymer into useful chemical b...

A number of ionic liquids have been shown to be excellent solvents for lignocellulosic biomass processing, and some of these are particularly effective in the production of the versatile chemical building block 5-hydroxymethylfurfural (HMF). In this study, the production of HMF from the simple sugar glucose in ionic liquid media is discussed. Sever...

Sample HPLC chromatograms shown in time course overlay. Peak 1 –glucose; peak 2 –fructose; peak 3—HMF. The trace is from the RI detectorwhich shows both HMF and the sugars. The UV/vis trace was used for quantification of HMF due to its higher sensitivity. (TIF)

Sample 1H NMR spectrum of the 30 minute reaction solution at 90°C. The mixture contained 0.1 g glucose, 0.7 g [C4C1im]Cl, 8.1 mol% CrCl3.6H2O. HMF signals appear at 7.5, 6.6, 4.9 and 4.5 ppm. (TIF)

Sample 1H NMR spectrum of 0.1 g 5-HMF in 0.7 g [C4C1im]Cl. (TIF)

Sample 1H NMR spectrumof [C4C1im]Cl. (TIF)

Time course overlay of 1H NMR spectra of reaction solution from 0–60 minutes at 90°C. 0.1 g glucose in 0.7 g [C4C1im]Cl with 8.1 mol% CrCl3.6H2O. At 0 min, two glucose signals are prominent in the area relevant for quantification, while these peaks dissappear as the reaction progresses (probably due to fast exchange) and the 4.5 ppm HMF peak appear...

Sample 1H NMR spectrum of 0.1 g glucose in 0.7 g [C4C1im]Cl. (TIF)

Sample 1H NMR spectrum of 0.1 g fructose in 0.7 g [C4C1im]Cl. (TIF)

A novel NHC–palladium(II) (NHC = N-heterocyclic carbene) complex and its immobilised version have been prepared and fully characterised. Optimisation studies led to good catalytic activities in Suzuki-Miyaura cross coupling and chloroarene dehalogenation reactions. Furthermore, the unexpected palladium-mediated transfer hydrogenation of a carbonyl...

The sensing of carbon monoxide (CO) using electrochemical cells or semiconducting metal oxides has led to inexpensive alarms for the home and workplace. It is now recognised that chronic exposure to low levels of CO also poses a significant health risk. It is perhaps surprising therefore that the CO is used in cell-signalling pathways and plays a g...

The HCl salt of the aminodiphosphine ligand HN(CH2CH2PPh2)2 reacts with [M(CO)4(pip)2] (M = Mo, W; pip = piperidine) to yield [M{κ(2)-HN(CH2CH2PPh2)2}(CO)4]. The molybdenum analogue readily loses a carbonyl ligand to form [Mo{κ(3)-HN(CH2CH2PPh2)2}(CO)3], which was structurally characterized. The same ligand backbone is used to form the new bifuncti...

The aza-crown ether compounds 1-aza-15-crown-5 and 1,10-diaza-18-crown-6 react with sodium hydroxide and carbon disulfide to provide the dithiocarbamates [15]aneO4-NCS2Na and NaS2CN-[18]aneO4-NCS2Na in good yield. The complexes [MRCl(CO)(L)(PPh3)2] (M = Ru, R = H, CH═CHC6H4Me-4, CH═CHBut, CH═CH-pyrenyl-1, C(C≡CPh)═CHPh; M = Os, R = H, CH═CH-pyrenyl...

The new, unsymmetrical dithiocarbamate ligands, KS2CN(CH2CH═CH2)Me and KS2CN(CH2C≡CH)Me, are formed from the respective amines on reaction with KOH and carbon disulfide. The homoleptic complexes [Ni{S2CN(CH2CH═CH2)Me}2] and [M{S2CN(CH2C≡CH)Me}2] (M = Ni, Pd, Pt) are formed on reaction with suitable metal precursors. Conversion between the two penda...

The artwork represents the detection of trace metals using SERS and a self-assembled nanoparticle film at a water/oil interface. The gold nanoparticles and mercury are shown entering the aqueous phase and assembling at the interface whilst the Raman reporter is entering from the oil phase. On page 966, J. D. E. T. Wilton-Ely, J. B. Edel, and co-wor...

The chromo-fluorogenic detection of carbon monoxide in air has been achieved using a simple, inexpensive system based on ruthenium(II). This probe shows exceptional sensitivity and selectivity in its sensing behavior in the solid state. A color response visible to the naked eye is observed at 5 ppb of CO and a remarkably clear color change occurs f...

A novel sensor for the detection of heavy metal ions in solution has been designed. It uses a recently developed new nanoplasmonic platform based on self-assembled layers of Au nanoparticles (NPs) at a liquid–liquid interface (LLI). This system is shown to be very promising for the detection of trace amounts of analyte molecules through their Raman...

The complexes [RuRCl(CO)(BTD)(PPh3)2] (R = CH=CHtBu, CH=CHC6H4Me-4, CH=CHC5H4FeC5H5; BTD = 2,1,3-benzothiadiazole) and [Ru{C(C≡CPh)=CHPh}(CO)(PPh3)2] reacted with pentynoic acid to yield the same complex, [RuCl(O2CCH2CH2C≡CH)(CO)(PPh3)2], through cleavage of the vinyl ligand. In contrast, the products [RuR(O2CCH2CH2C≡CH)(CO)(PPh3)2] were formed whe...

The room-temperature ionic liquid, [C4C1im][HSO4], provides a multi-faceted medium in which to convert fructose to the versatile chemical building block, 5-hydroxymethylfurfural (HMF). A range of metal salts have been investigated in order to establish some of the properties required for the optimization of this process. This has led to almost quan...

The gold(I) complexes [Au{S2CN(CH2CH═CH2)2}(L)] [L = PPh3, PCy3, PMe3, CN(t)Bu, IDip] are prepared from KS2CN(CH2CH═CH2)2 and [(L)AuCl]. The compounds [L2(AuCl)2] (L2 = dppa, dppf) yield [(L2){AuS2CN(CH2CH═CH2)2}2], while the cyclic complex [(dppm){Au2S2CN(CH2CH═CH2)2}]OTf is obtained from [dppm(AuCl)2] and AgOTf followed by KS2CN(CH2CH═CH2)2. The...

Immobilised [Cu(NHC)] catalysts are reported for the preparation of 1,2,3-triazoles. In addition to showing outstanding catalytic activity, the catalyst systems are easy to prepare and can be recycled many times.

The versatile precursors [Ru(CH═CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole) and [Ru(C(C≡CPh)═CHPh)Cl(CO)(PPh3)2] were treated with isonicotinic acid, 4-cyanobenzoic acid, and 4-(4-pyridyl)benzoic acid under basic conditions to yield [Ru(vinyl)(O2CC5H4N)(CO)(PPh3)2], [Ru(vinyl)(O2CC6H4CN-4)(CO)(PPh3)2], and [Ru(vinyl){O2CC6H4(C5H4N...

The palladium(ii) dimer, [Pd(C,N-C(6)H(4)CH(2)NMe(2))Cl](2) reacts with two equivalents of the NHC·CS(2) zwitterionic ligands [NHC = IPr (1,3-diisopropylimidazol-2-ylidene), ICy (1,3-dicyclohexylimidazol-2-ylidene), IMes (1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), IDip (1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), SIMes (1,3-bis(2,4,6...

The ruthenium(II) complexes [Ru(CHCHR){κ2-S2P(OEt)2}(CO)(PPh3)2] (R = But, C6H4Me-4) are formed on reaction of (NH4)[S2P(OEt)2] with [Ru(CHCHR)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole), while the enynyl complex [Ru(C(CCPh)CHPh)Cl(CO)(PPh3)2] loses a phosphine on treatment with the same ligand to yield [Ru(η3-PhCC–CCHPh){κ2-S2P(OEt)2}(CO)(P...

The new 2-phenylthiocarbamoyl-1,3-dimesitylimidazolium inner salt (IMes·CSNPh) reacts with [AuCl(L)] in the presence of NH(4)PF(6) to yield [(L)Au(SCNPh·IMes)](+) (L = PMe(3), PPh(3), PCy(3), CNBu(t)). The carbene-containing precursor [(IDip)AuCl] reacts with IMes·CSNPh under the same conditions to afford the complex [(IDip)Au(SCNPh·IMes)](+) (IDip...

The ruthenium(II) complexes [Ru(R)(κ(2)-S(2)C·IPr)(CO)(PPh(3))(2)](+) (R = CH=CHBu(t), CH=CHC(6)H(4)Me-4, C(C≡CPh)=CHPh) are formed on reaction of IPr·CS(2) with [Ru(R)Cl(CO)(BTD)(PPh(3))(2)] (BTD = 2,1,3-benzothiadiazole) or [Ru(C(C≡CPh)=CHPh)Cl(CO)(PPh(3))(2)] in the presence of ammonium hexafluorophosphate. Similarly, the complexes [Ru(CH=CHC(6)...

The ligands KS(2)CN(Bz)CH(2)CH(2)N(Bz)CS(2)K (K(2)L(1)), N(CH(2)CH(2)N(Me)CS(2)Na)(3) (Na(3)L(2)), and the new chelates {(CH(2)CH(2))NCS(2)Na}(3) (Na(3)L(3)) and {CH(2)CH(2)N(CS(2)Na)CH(2)CH(2)CH(2)NCS(2)Na}(2) (Na(4)L(4)), react with the gold(I) complexes [ClAu(PR(3))] (R = Me, Ph, Cy) and [ClAu(IDip)] to yield di-, tri-and tetragold compounds. La...

A range of new nickel, copper and zinc bis(dithiocarbamate) complexes has been prepared from secondary amines with functionalised backbones. These include complexes derived from iso-indoline, tetrahydro-isoindoline, 1,2,3,4-tetrahydroisoquinoline and a number of functionalised piperazines. The crystal structure of [Ni(S2CNC3H6C6H4)2] derived from 1...

Not so innocent: Sterically tuneable dithiocarboxylate ligands derived from N-heterocyclic carbenes act as excellent bidentate chelates for ruthenium(II) σ-alkenyl complexes. However, the most sterically demanding member of the ligand family causes a fascinating and unexpected rearrangement to occur (see figure; ICy=1,3-dicylohexylimidazolium, IDip...

We have developed a methodology for the in situ derivatisation of histidine residues in self-assembled monolayers of peptides with redox-active groups, and have shown by electrochemical methods that the average dipole of peptide films on gold affects the heterogeneous electron transfer properties.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

The complex cis-[RuCl2(dppm)2] reacts with the diallyldithiocarbamate KS2CN(CH2CH═CH2)2 to form [Ru{S2CN(CH2CH═CH2)2}(dppm)2]+. The same ligand was also used to prepare the alkenyl complexes [RuR{S2CN(CH2CH═CH2)2}(CO)(PPh3)2] (R = CH═CHBut, CH═CHC6H4Me-4, C(C≡CBut)═CHBut) from the corresponding precursors [RuRCl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzot...

The complex cis-[RuCl(2)(dppm)(2)] reacts with the amine-terminated dithiocarbamates KS(2)CN(CH(2)CH(2)NEt(2))(2) and KS(2)CN(CH(2)CH(2)CH(2)NMe(2))(2) to form the compounds [Ru{S(2)CN(CH(2)CH(2)NEt(2))(2)}(dppm)(2)](+) and [Ru{S(2)CN(CH(2)CH(2)CH(2)NMe(2))(2)}(dppm)(2)](+), respectively. The methoxy-terminated dithiocarbamate compound [Ru{S(2)CN(C...

The imidazolium-2-dithiocarboxylate ligands IPr.CS(2), IMes.CS(2), and IDip.CS(2) react with [AuCl(PPh(3))] to yield [(Ph(3)P)Au(S(2)C.IPr)](+), [(Ph(3)P)Au(S(2)C.IMes)](+), and [(Ph(3)P)Au(S(2)C.IDip)](+), respectively. The compounds [(L)Au(S(2)C.IMes)](+) are prepared from the reaction of IMes.CS(2) with [AuCl(L)] (L = PMe(3), PCy(3), CN(t)Bu). T...

The reaction of [RhCl(PPh3)3] with [9]aneS3 (1,4,7-trithiacyclononane) and NH4PF6 provides [Rh(PPh3)2([9]aneS3)PF6, which undergoes ligand subsitution and oxidative-addition reactions and effectively catalyzes the demercuration of bis(alkynyl)mercurials.

The homobimetallic ruthenium(II) and osmium(II) complexes [{RuR(CO)(PPh(3))(2)}(2)(S(2)COCH(2)C(6)H(4)CH(2)OCS(2))] (R = CH=CHBu(t), CH=CHC(6)H(4)Me-4, C(C[triple bond]CPh)=CHPh, CH=CHCPh(2)OH) and [{Os(CH=CHC(6)H(4)Me-4)(CO)(PPh(3))(2)}(2)(S(2)COCH(2)C(6)H(4)CH(2)OCS(2))] form readily from the reactions of [MRCl(CO)(BTD)(PPh(3))(2)] (M = Ru or Os;...

Homobimetallic complexes of nickel, palladium and platinum, [(L2M)2(S2CNC4H8NCS2)]2+, are formed on reaction of the piperazine bis(dithiocarbamate) linker, KS2CNC4H8NCS2K, with [MCl2L2] (M=Ni, L2=dppe, dppf; M=Pd, L2=dppf; M=Pt, L=PEt3, PMePh2, PPh3, L2=dppf). [{Pd(C,N-C6H4CH2NMe2)}2(S2CNC4H8NCS2)] can be obtained in the same way. On reaction of [M...

The amine-functionalised dithiocarbamate salts K[S2CN(CH2CH2NEt2)2] and K[S2CN(CH2CH2CH2NMe2)2] have been prepared and used for the synthesis of a number of bis and tris-dithiocarbamate complexes. The molecular structures of five of these namely, [M{S2CN(CH2CH2NEt2)2}2] (M = Cu, Ni), [M{S2CN(CH2CH2CH2NMe2)2}2] (M = Cu, Pd) and [Co{S2CN(CH2CH2CH2NMe...

Reaction of [AuCl(PPh(3))] with the zwitterion S(2)CNC(4)H(8)NH(2) yields [(Ph(3)P)Au(S(2)CNC(4)H(8)NH(2))]BF(4). Treatment of this species with NEt(3) and CS(2) followed by [AuCl(PPh(3))] leads to [{(Ph(3)P)Au}(2)(S(2)CNC(4)H(8)NCS(2))], which can also be obtained directly from [AuCl(PPh(3))] and KS(2)CNC(4)H(8)NCS(2)K. A heterobimetallic variant,...

A dithiocarbamate-based methodology is employed to prepare linked heteromultimetallic complexes and then further exploited in the surface functionalisation of gold nanoparticles.

The cationic complex [Ru(C(C CPh) CHPh)(S,CNC(4)HgNH(2))(CO)(PPh(3))(2)](+) was prepared from the reaction of [Ru(C(C CPh)=CHPh)Cl(CO)(BTD)(PPh(3))(2)] (BTD = 2,1,3-benzothiadiazole) with the zwitterionic dithiocarbamate H,NCANCS, and characterized structurally. In situ generation of the metal lad ithiocarbamate [Ru(C(C CPh)=CHPh)(SCNC(4)H(8)NCS(2)...

The reactions of a range of coordinatively unsaturated σ-organyl thiocarbonyl complexes with 1,4,7-trithiacyclononane ([9]aneS3) have been investigated, leading in some but not all cases to migratory insertive coupling of thiocarbonyl and σ-organyl ligands. Thus, under ambient conditions, the reaction of [RuR-Cl(CS)(PPh3)2] (R = C(CO2Me)=CHCO2Me, C...

Treatment of cis-[RuCl2(dppm)2] (dppm = bis(diphenylphosphino)methane) with dithiocarbamates, NaS2CNR2 (R = Me, Et) and [H2NC5H10][S2CNC5H10], yields cations [Ru(S2CNR2)2(dppm)2](+) and [Ru(S2CNC5H10)2(dppm)2](+), respectively. The zwitterions S2CNC4H8NHR (R = Me, Et) react with the same metal complex in the presence of base to yield [Ru(S2CNC4H8NR...

Assembly of dodecyl thiocyanate (C12SCN) from ethanol solution onto Au(111)/mica substrates was investigated by scanning tunneling microscopy (STM), near edge X-ray absorption fine structure spectroscopy (NEXAFS), X-ray photoelectron spectroscopy (XPS), and infrared reflection-absorption spectroscopy (IRRAS). Contrary to previous reports, thiolate...

The use of nanoparticles is now expanding well beyond the field of pure materials science. In particular, the modification of the surface functionality is playing a key role in catalysis, sensor applications and immobilisation of biomolecules. The use of coordinated metals on the outer surface of gold nanoparticles is the focus of this short articl...

The reactions of [RuHCl(CS)(PPh3)(3)] with (RC)-C-1 CR2 (R-1 = R-2 = H, Ph, CO2Me; R-1 = H, R-2 = C6H4Me-4; R-1 = C CPh, R-2 = Ph) lead to the five- or six-coordinate (R-1 = R-2 = CO2Me) sigma-alkenyl complexes [Ru(CR1=CHR2)Cl(CS)(PPh3)(2)], the stilbenyl derivative being also formed by thermolysis of [RuCl(kappa(2)-O2CH)(CS)(PPh3)(2)] in the prese...

Self-assembled monolayers (SAMs) of two omega-(4'-methylbiphenyl-4-yl)alkanethiols (CH(3)(C(6)H(4))(2)(CH(2))(n)SH, BPn, n = 4, 6) on Au(111) substrates, prepared from solution at room temperature and subsequently annealed at temperatures up to 493 K under a nitrogen atmosphere, were studied using scanning tunneling microscopy (STM), high-resolutio...

A series of molecules bearing both sulfur and nitrogen donors has been investigated as ligands for σ-alkenyl ruthenium complexes. On deprotonation, the ligands, 4-amino-2-mercaptopyrimidine (HL1), 2-amino-5-mercapto-1,3,4-thiadiazole (HL2), 2-mercaptothiazoline (HL3), 4-hydroxy-2-mercaptopyrimidine (HL4) and 2-mercaptoquinoline (HL5) all react with...

Reaction of cis-[RuCl2(dppm)2] (dppm = bis(diphenylphosphino)methane) with CS2 and NaOH yields the first ruthenium dithiocarbonate complex, [Ru(kappa2-S2C=O)(dppm)2]. Protonation with tetrafluoroboric acid affords the xanthate complex [Ru(kappa2-S2COH)(dppm)2]BF4 in a reversible manner, suggesting that this may be an intermediate in dithiocarbonate...

The zwitterionic piperazine-derived dithiocarbamate complex [(dppm)(2)Ru(S(2)CNC(4)H(8)NCS(2))] has been prepared and utilised in the synthesis of multimetallic arrays incorporating a wide range of transition metal centres. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.

The reaction of [Ru(CO)2(PPh3)3] (1) or [Ru(η2-CS2)(CO)2(PPh3)2] with N,N-dimethylthiocarbamoyl chloride provides [Ru(η2-SCNMe2)(CO)2(PPh2)2]Cl (2·Cl), thermolysis of which yields [Ru(η2-SCNMe2)Cl(CO)(PPh2)2] (3). Treatment of 2·Cl with NaBH4 leads to carbonyl substitution and formation of [RuH(η2-SCNMe2)(CO)(PPh3)2] (4), which is readily converted...

The Schiff base, 2-chlorophenylsalicylaldimine (HL1), is formed readily from salicylaldehyde and 2-chloroaniline. After deprotonation, this ligand is found to react as a bidentate mixed-donor chelate with the complexes [RuRCl(CO)(BTD)(PPh3)2] (R = H, CHCHC6H5, CHCHC6H4Me-4, CH=CHtBu, CC=CPh=CHPh; BTD = 2,1,3-benzothiadiazole) to form the compounds...

Self-assembled monolayers of omega-(4'-methylbiphenyl-4-yl) alkane thiols CH3(C6H4)2(CH2)(n)SH (BPn, n = 2, 3, and 5) on Au(111) substrates, prepared at room and elevated temperatures, were studied using scanning tunneling microscopy. In contrast to the biphenyl thiol analogues with n = 0 or 1, ordered domains of large size are formed which exhibit...

A series of vinyl, aryl, acetylide and silyl complexes [Ru(R)(kappa2-MI)(CO)(PPh3)2] (R = CH=CH2, CH=CHPh, CH=CHC6H4CH3-4, CH=CH(t)Bu, CH=2OH, C(C triple bond CPh)=CHPh, C6H5, C triple bond CPh, SiMe2OEt; MI = 1-methylimidazole-2-thiolate) were prepared from either [Ru(R)Cl(CO)(PPh3)2] or [Ru(R)Cl(CO)(BTD)(PPh3)2](BTD = 2,1,3-benzothiadiazole) by r...

The reactions of the iridaphosphirene complex [Ir{=C(tBu)P(Cy)}(CO)(PPh3)2] (Cy = cyclohexyl) with either [AuCl(tht)] (tht = tetrahydrothiophene) or AgCl result in the products [Ir{=C(tBu)P[M(Cl)](Cy)}(CO)(PPh3)2], M = Au or Ag. The aurated product can additionally be obtained on reaction of the iridaphosphirene with [AuCl(CNtBu)], via loss of the...

Vilsmair salts have been used to prepare a series of thioaldehyde molecules conjugated with a pyrrole ring (pyrrole substituents:  H, Me, Et). The reaction of 3,5-dimethyl-4-ethylpyrrole-2-carbothioaldehyde (HL4) with [RuHCl(CO)(PPh3)3] or [RuHCl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole) in the presence of NaOMe leads to the complex [RuH(κ2-L...

The coordination chemistry of the unusual, pyrrole-stabilised thioaldehyde molecules, 3,5-dimethylpyrrole- 2-carbothioaldehyde (HSPyMeHMe) and 3,5-dimethyl-4-ethylpyrrole-2-carbothioaldehyde (HSPyMeEtMe) has been investigated with nickel, palladium and platinum in the complexes [M(κ2- SPyMeRMe)2] (M = Ni, Pd, Pt; R = H, Et). The structure of the cy...

Cobalt complexes involved in the hydroformylation of alkenes using (4R,S)-4,8-dimethyl-2-octadecyl-2-phospha-bicyclo[3.3.1]nonane (LIM-18), which consists of a mixture of two diastereomers, have been studied. Complexation to cobalt has been used to separate or enrich the enantiomers so that spectroscopic parameters can be determined for complexes o...

Treatment of the gold(I) halide complexes LAuCl (where L=PMe3, PEt3, PPh3, PPh2Py) and PP(AuCl)2 [where PP=bis(diphenylphosphino)methane; 1,1′-bis(diphenylphosphino)ferrocene] with 4-amino-2-pyrimidine-thiol (2-SPym-4-NH2) (one or two equivalents as required) in the presence of sodium methoxide provides the corresponding (phosphine)gold(I) thiolate...

Treatment of silver(I) bromide with the ligands [Ph2P(Se)HNP(E)Ph-2] (E = Se, S or O) and [Ph2P(Se)HNPPh2] results in the formation of the salts [{HN(Ph2PSe)(2)-Se,Se'}(2)Ag]Br, [{HN(Ph2PSe)(Ph2PS)-Se,S}(2)Ag]Br, [{HN(Ph2PSe)(Ph2PO)-Se}(2)Ag]Br and [{HN(Ph2PSe)(Ph2P)-Se,P}(2)Ag]Br, respectively. From analysis of spectroscopic data, it appears that...

A series of dinuclear (phosphine)gold(I) complexes of the ambidentate 1,3,4-thiadiazoledithiolate ligand (SSS) were prepared in high yield from the corresponding (phosphine)gold(I) chlorides and K(2)(SSS) in methanol. While mononuclear components (R(3)P)AuCl with R(3) = Ph(3), Ph(2)Py, or Me(3) (1-3) gave open-chain complexes, the dinuclear compone...

Treatment of the ligand 1,3,5-tris[(diphenylphosphanyl)methyl]trimethylbenzene (P3) with (tetrahydrothiophene)gold(I) chloride results in the symmetrical trigold complex [(P3)(AuCl)3]. In the presence of sodium methoxide, [(P3)(AuCl)3] reacts with thiocresol (HSC6H4Me-4) and 2-mercaptoquinoline (2-HSQn) to provide the complexes [(P3)(AuSC6H4Me-4)3]...

Treatment of the (isocyanide)gold(I) species LAuCl (L=tBuNC, 2,6-Me2C6H3NC) with 4-mercaptobenzoic acid in the presence of NaOMe yields the complexes [Au(4-SC6H4CO2H)L] in good yield. Reaction of LAuCl with 2-HSQn (Qn=quinoline) and 2-HSPy (Py=pyridine) under the same conditions provides the thiolato compounds [Au(2-SQn)L] and [Au(2-SPy)L], respect...

Treatment of the gold(I) halide complexes LAuCl (L = PMe3, PPh3, CNC6H3Me2-2,6) with K[Ph2P(Se)NP(Se)Ph2] provides the gold-selenium coordination compounds [(N(Ph2PSe)2-Se,Se')AuL]. However, on standing for a number of days, the complex [(N(Ph2PSe)2-Se,Se')AuPMe3] gains a phosphine to provide the bis(phosphine) species [(N(Ph2PSe)2-Se,Se')Au(PMe3)2...

Treatment of 2 molar equiv of ((BuNC)-Bu-t)AuCl with I equiv of the dipotassium salt of 2,5-dimercapto-1,3,4-thiadiazole, K-2(SSS), results in the formation of the crystalline product [((BuNC)-Bu-t)Au](2)(SSS) in addition to polymeric material. A crystallographic study reveals a complex supramolecular structure for the crystalline product resemblin...

Treatment of the gold(I) halide species AuLCl (where L = PMe3, PEt3, PPh3, PPh2(C5H4N-2) or SPPh3) and (AuCl)2(P–P) (where P–P = 1,4-bis(diphenylphosphino)butane or 1,1′-bis(diphenylphosphino)ferrocene) with 4-sulfanylbenzoic acid (1 or 2 equivalents as required) in the presence of sodium methoxide provided the corresponding phosphine gold(I) thiol...

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and...

The well defined, conveniently accessible and coordinatively unsaturated allenylidene complexes [RuCl2(CC CPh2)(PCy3)2] and [Ru2Cl4(CCCPh2)(PCy3)(η-MeC6-H4Pri-4)] are highly effective catalysts for the ambient temperature ring-closure metathesis of α,ω-dienes and dienynes, illustrated by the facile and high yielding formation of variously functiona...

The reaction of [RuCl(PPh3)2{HB(pz)3}] (pz=pyrazol-1-yl) with 4-ethynyl toluene provides [RuCl(CCHC6H4Me-4)(PPh3){HB(pz)3}] (1a) which reacts with [Et2NH2][S2CNEt2] to give the metallacyclic alkenyl complex [Ru{C(CHC6H4Me-4)SC(NEt2)S}(PPh3){HB(pz)3}] (2). The reaction of [RuCl(PPh3)2{HB(pz)3}] with diphenylpropynol and Ag[PF6] however provides [...

The substitution chemistry of the complex [RuCl(PPh3)(2){HB(pz)(3)}] (1) is reported. Treating 1 with the phosphines bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), or 1,1'-bis(diphenylphosphino)ferrocene (dppf) provides the complexes [RuCl(dppm){HB(pz)(3)}] (2), [RuCl(dppe){HB(pz)(3)}] (3), or [RuCl(dppf){HB(pz)(3)}]...

The reaction of [OsHCl(CO)(PPh3)2(BTD)] (BTD = 2,1,3-benzothiadiazole) with PCCMe3 provides the novel complex [Os{κ1P,κ1P′-PCRP(CHR)Cl(CO)(PPh3)2] (R = CMe3) which features both phospha-alkenyl and phospha-alkene donors within the same metallacycle.

The reactions of [MCl2(PPh3)3] with HCCCPh2OH provided [MCl2(CCCPh2)(PPh3)2] (M = Ru 1a or Os 1b) the first examples of co-ordinatively unsaturated allenylidene complexes of Group 8 metals. The phosphine ligands of 1a are labile and readily replaced by PCy3 to give [RuCl2(CCCPh2)(PCy3)2] 1c. Heating 1a with NaPF6 in chloroform gave the known bimeta...

Treatment of [OsH(CA)(NCMe)2(PPh3)2]+ (A = O or S) with [NEt4]Cl and 2,1,3-benzothiadiazole (BTD) provided [OsH(Cl)(CA)(BTD)(PPh3)2] (A = O or S). Under mild conditions, the complex [OsH(Cl)(CO)(BTD)(PPh3)2] hydro-osmiates ethynyltoluene, ethyne and di(4-tolyl)butadiyne to provide vinyl complexes [Os(CHCHR)Cl(CO)(BTD)(PPh3)2] (R = C6H4Me-4), [Os(CH...

The reaction of [RuHCl(CO)(PPh3)3] (1a) with PCCMe3 results in the formation of the phosphaalkenyl complex [Ru(PCHCMe3)Cl(CO)(PPh3)2] (2a). Being coordinatively unsaturated, 2a reacts reversibly with CO to provide [Ru(PCHCMe3)Cl(CO)2(PPh3)2] (3) and with isonitriles (CNR) to provide [Ru(PCHCMe3)Cl(CNR)(CO)(PPh3)2] [R = CMe3 (4a), C6H3Me2-2,6 (4b)]....

Treatment of either [RuHCl(CO)(PPh3)(3)] or [RuH(CO)(NCMe)(2)(PPh3)(2)]BF4 with K[H2B-(pz)(2)] (pz = pyrazol-1-yl) provides [RuH(CO)(PPh3)(2){H2B(pz)(2)}] (1), which is also the product of the reaction of [Ru(SnPh3)Cl(CO)(PPh3)(2)] or [Ru(SiMe3)Cl(CO)(PPh3)(2)] with K[H2B(pz)(2)] in the presence of ethanol. The complexes [RuHCl(CS)(BTD)(PPh3)(2)] (...

The new complex [TpRh(PPh3)2], readily obtained from [RhCl(PPh3)3] and KTp, is a particularly convenient and versatile entry point into the organometallic chemistry of the “TpRh” fragment including complexes bearing alkyne, alkene, carbene, thiocarbamoyl, dithioalkoxycarbonyl, carbon disulfide, and vinyl ligands.

Stable complexes of mercuriophosphaalkenes have resulted from the addition of organomercury halides to the Ru–P bond of [Ru(PCHBut)Cl(CA)(PPh3)2] (A = O or S), including the structurally characterised complex [Ru{P(CHBut)HgC5H4Fe(η-C5H5)}Cl2(CO)(PPh3)2].

[RuHCl(CO)(PPh3)3], [Ru(SnPh3)Cl(CO)(PPh3)2], or [RuH(CO)(NCMe)2(PPh3)2]BF4 reacts with K[HB(pz)3] (pz = pyrazol-1-yl) to provide [RuH(CO)(PPh3)2{η2-HB(pz)3}], thermolysis of which proceeds via loss of phosphine and formation of [RuH(CO)(PPh3){η3-HB(pz)3}]. The thiocarbonyl analogue [RuH(CS)(PPh3)2{η2-HB(pz)3}] is obtained from [RuHCl(CS)(PPh3)3] a...

The reaction of [Ru(PCHBut)Cl(CO)(PPh3)2] 1 or [Ru(PCHBut)Cl(CNBut)(CO)(PPh3)2] 2b with excess pivalo isonitrile under aerobic conditions provides the novel metallacyclic λ5-phosphaalkenyl-P complex [Ru{κ2-P(O)CButC(O)}(CNBut)2(PPh3)2], which has been crystallographically characterised.

The reaction of [Ru(CO)2(PPh3)3] (1) with P⋮CtBu is complex; however, under the same conditions 1 with P⋮CR‘ (R‘ = C6H2tBu3-2,4,6) provides the complex [Ru(σ-P⋮CR‘)(CO)2(PPh3)2], spectroscopic data for which are consistent with monohapto σ-P coordination.

The reaction of [RhCl(PPh3)3] with [9]aneS3 (1,4,7-trithiacyclononane) and NH4PF6 provides [Rh(PPh3)2([9]aneS3)]PF6, which undergoes ligand subsitution and oxidative-addition reactions and effectively catalyzes the demercuration of bis(alkynyl)mercurials.

The reaction of [Ru(PCHBu t )Cl(CE)(PPh 3 ) 2 ] (E = O, S) with [AuX(PPh 3 )] (X = Cl, CCC 6 H 4 Me-4), HgCl 2 or Hg 2 Cl 2 leads via addition of the Au–X or Hg–Cl bonds across the Ru–P linkage to the heterodinuclear phosphaal- kene complexes [Ru{P(AuPPh 3 )CHBu t }ClX(CE)(PPh 3 ) 2 ] and [Ru{P(HgCl)CHBu t }Cl 2 (CE)(PPh 3 ) 2 ].

The reaction of [Ru(CHCH2)Cl(CO)(PPh3)2] with diazomethane provides the allyl complex [Ru(η3-CH2CHCH2)Cl(CO)(PPh3)2] which is also the product of the reactions of [RuHCl(CO)(PPh3)3] with either allene or propyne and which reacts subsequently with NaS2CNMe2 to provide [RuH(S2CNMe2)(CO)(PPh3)2] and allene.

The reaction of coordinatively unsaturated σ-vinyl complexes [Ru(CRCHR‘)Cl(CO)(PPh3)2] with 1,4,7-trithiacyclononane ([9]aneS3) provides chiral salts of the “half-sandwich” complexes [Ru(CRCHR‘)(CO)(PPh3)([9]aneS3)]+. The synthesis of the σ-aryl complex [Ru(C6H4Me-4)(CO)(PPh3)([9]aneS3)]+ is also described. A representative NMR study of one example...

Treating [IrCl(CO)(PPh3)2] with ClC(=S)OR (R = C6H4Me-4) provides [IrCl2{C(=S)OR}-(CO)(PPh3)2], which reacts with NaBH4 to give [IrHCl{C(=S)OR}(CO)(PPh3)2]. The aryloxide group is cleaved by HCl to give [IrHCl2(CS)(PPh3)2], which is dehydrochlorinated by DBU to provide [IrCl(CS)(PPh3)2] (overall yield for "Ir(CO)" → "Ir(CS)" 75%). Treating [IrCl(CS...