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Background: Clinical variables—age, family history, genetics—are used for prostate cancer risk stratification. Recently, polygenic hazard scores (PHS46, PHS166) were validated as associated with age at prostate cancer diagnosis. While polygenic scores are associated with all prostate cancer (not specific for fatal cancers), PHS46 was also associated with age at prostate cancer death. We evaluated if adding PHS to clinical variables improves associations with prostate cancer death. Methods: Genotype/phenotype data were obtained from a nested case-control Cohort of Swedish Men (n=3,279; 2,163 with prostate cancer, 278 prostate cancer deaths). PHS and clinical variables (family history, alcohol intake, smoking, heart disease, hypertension, diabetes, body mass index) were tested via univariable Cox proportional hazards models for association with age at prostate cancer death. Multivariable Cox models with/without PHS were compared with log-likelihood tests. Results: Median age at last follow-up/prostate cancer death were 78.0 (IQR: 72.3–84.1) and 81.4 (75.4–86.3) years, respectively. On univariable analysis, PHS46 (HR 3.41 [95%CI 2.78–4.17]), family history (HR 1.72 [1.46–2.03]), alcohol (HR 1.74 [1.40–2.15]), diabetes (HR 0.53 [0.37–0.75]) were each associated with prostate cancer death. On multivariable analysis, PHS46 (HR 2.45 [1.99–2.97]), family history (HR 1.73 [1.48–2.03]), alcohol (HR 1.45 [1.19–1.76]), diabetes (HR 0.62 [0.42–0.90]) all remained associated with fatal disease. Including PHS46 or PHS166 improved multivariable models for fatal prostate cancer (p

BackgroundClinical variables—age, family history, genetics—are used for prostate cancer risk stratification. Recently, polygenic hazard scores (PHS46, PHS166) were validated as associated with age at prostate cancer diagnosis. While polygenic scores are associated with all prostate cancer (not specific for fatal cancers), PHS46 was also associated with age at prostate cancer death. We evaluated if adding PHS to clinical variables improves associations with prostate cancer death.MethodsGenotype/phenotype data were obtained from a nested case-control Cohort of Swedish Men (n=3,279; 2,163 with prostate cancer, 278 prostate cancer deaths). PHS and clinical variables (family history, alcohol intake, smoking, heart disease, hypertension, diabetes, body mass index) were tested via univariable Cox proportional hazards models for association with age at prostate cancer death. Multivariable Cox models with/without PHS were compared with log-likelihood tests.ResultsMedian age at last follow-up/prostate cancer death were 78.0 (IQR: 72.3-84.1) and 81.4 (75.4-86.3) years, respectively. On univariable analysis, PHS46 (HR 3.41 [95%CI 2.78-4.17]), family history (HR 1.72 [1.46-2.03]), alcohol (HR 1.74 [1.40-2.15]), diabetes (HR 0.53 [0.370.75]) were each associated with prostate cancer death. On multivariable analysis, PHS46 (HR 2.45 [1.99-2.97]), family history (HR 1.73 [1.48-2.03]), alcohol (HR 1.45 [1.19-1.76]), diabetes (HR 0.62 [0.42-0.90]) all remained associated with fatal disease. Including PHS46 or PHS166 improved multivariable models for fatal prostate cancer (p-15).ConclusionsPHS had the most robust association with fatal prostate cancer in a multivariable model with common risk factors, including family history.ImpactAdding PHS to clinical variables may improve prostate cancer risk stratification strategies.

The reaction of N-phenyltriazolinedione with three simple alkyl-substituted alkenes in water/alcohol or water/acetone solution was found to give a mixture or the corresponding ene and water addition products. The new hydration products were characterized by spectroscopy, and in one case, also by X-ray diffraction analysis. Thermodynamic parameters were determined for the reactions involving 2-methylbut-2-ene, TriME, and 2,3-dimethylbut-2-ene, TetraMe, in accordance with an 'S(N)2-like', nucleophilic attack on a closed aziridinium imide (At) intermediate by water. (C) 2008 Elsevier Ltd. All rights reserved. Tetrahedron Lett

A synthesis of new bidentate pyridines 8a–d, 9, and 10 has been developed, starting from triflate 14, readily available from β-pinene 11. A copper complex of the pyridine–oxazoline ligands 8a has been found to catalyze asymmetric allylic oxidation of cyclic olefins 36a–c with good conversion rates and acceptable enantioselectivity (≤67% ee). The imidazolium salt 10 has been identified as a precursor of the corresponding N,N′-unsymmetrical N-heterocyclic carbene ligand, whose complex with palladium catalyzed the intramolecular amide enolate α-arylation leading to oxindole 45 in excellent yield but with low enantioselectivity.

Mixed μ-phosphido or μ-thiolato μ-halo-dimolybdenum(III) compounds [Mo 2 Cp 2 (μ-SMe) 2 (μ-X)(μ-Y)] (X = PPh 2 , Y = Cl ( 1 ); X = SCH 3 , Y = Br ( 3 ), I( 4 )) have been studied. Syntheses and X-ray structures of the new bromo and iodo analogues of [Mo 2 Cp 2 (μ-SMe) 3 (μ-Cl)] ( 2 ) are reported. While preparing 3 a side-product 5 was obtained and structurally characterised as the Mo 5 system [{Mo 2 Cp 2 Br(μ-O)(μ-SMe) 2 } 2 (μ-MoO 4 )], containing a {Mo IV –Mo IV –O–(Mo VI O 2 )–O–Mo IV –Mo IV } unit. The influence of the bridging groups on the structures and electrochemical behaviour of the complexes [Mo 2 Cp 2 (μ-SMe) 2 (μ-X)(μ-Y)] 1 – 4 has been investigated. In MeCN–[NBu 4 ][PF 6 ] the first oxidation of [Mo 2 Cp 2 (μ-SMe) 2 (μ-PPh 2 )(μ-Cl)] ( 1 ) is quasi-reversible, contrasting with the essentially irreversible first oxidation of the thiolate analogue [Mo 2 Cp 2 (μ-SMe) 3 (μ-Cl)] ( 2 ) under similar conditions. The effects of lowering the temperature or increasing the scan rate on the oxidation of 1 were examined: the initial quasi-reversible oxidation at first became irreversible but at still higher scan rates or lower temperatures the oxidation was again quasi-reversible. This suggests that the oxidation of 1 in MeCN is followed by reversible coordination of acetonitrile to afford the species [Mo 2 Cp 2 (μ-SMe) 2 (μ-PPh 2 )(Cl)(MeCN)] + ( 7 + ). Cyclic voltammetry of [Mo 2 Cp 2 (μ-SMe) 3 (μ-Y)](Y = Br ( 3 ) or I ( 4 )) showed two quasi-reversible diffusion-controlled oxidation steps in CH 2 Cl 2 –[NBu 4 ][PF 6 ] or thf–[NBu 4 ][PF 6 ]. In acetonitrile, the fast loss of the halide ligands results in the formation of [Mo 2 Cp 2 (μ-SMe) 3 (MeCN) 2 ] + species.

Attempts at methylating cis -[Mo 2 Cp 2 (μ-SMe) 3 L 2 ](BF 4 ) [Cp = η 5 -C 5 H 5 ; L = CO ( 1a ) CNxyl ( 1b ), CNBu t ( 1c ), NCMe ( 1d )] with methyl triflate gave the corresponding thioether-bridged cations [Mo 2 Cp 2 (μ-SMe) 2 (μ-SMe 2 )L 2 ] 2+ ( 4 2+ ), except in the case of 1a which did not react at room temperature. The electronic properties of the ancillary ligands L thus have a crucial influence on the course of this reaction. The dimeric compounds [Mo 2 Cp 2 (μ-SMe) 3 (CNBu t )(CN)] ( 2 ) and [Mo 2 Cp 2 (μ-SMe) 3 {μ-η 1 -N C(CH 3 )CH 2 CN}] ( 3 ), which potentially offer the alternatives of S- or N-methylation, reacted with methylating agents to give mainly the S-methylated derivatives 5 and 7 . Only in the case of the nucleophilic reactant 2 was N-methylation also observed and isomer 6 was obtained as a minor product together with 5 . New complexes have been completely characterised by multinuclear NMR, IR and elemental analysis, supplemented for 5 by X-ray diffraction study at 100 K.

cited By 10; International audience; A series of chemical and electrochemical transformations of systems in which a Mo2Cp2(μ-SMe)3 core is bridged by a μ-C2HnR ligand (n = 0-4) are described in this paper. The reaction of the alkylidene complex [Mo2Cp2(μ-SMe) 3(μ-η1:η2-CHCH2Tol)] (BF4) (1) with LiBun at 0°C produces the μ-σ,π-vinyl complex [Mo2Cp2(μ-SMe) 3(μ-η1:η2-CH=CHTol] (2) in good yield. The molecular structure of 2 has been confirmed by X-ray analysis. Upon treatment with NaBEL4 1 is readily converted into the semibridging alkyl species [Mo2Cp2(μ-SMe)3(μ-CH 2CH2Tol)] (3), which is also formed by electrochemical reduction of 1 in acidic medium. NMR and X-ray diffraction studies of 3 are consistent with, but do not definitively establish, the presence of a η1 α-agostic interaction. Density functional theory has been used to confirm the presence of agostic interactions in both 1 and 3 and also to explore the exchange pathways for these hydrocarbyl dimolybdenum systems. Electrochemical transformation of the μ-alkylidene complex 1 gives 3 as the major product when acid is present and a mixture of 2 and 3 when acid is absent, production of 2 being favored by low initial concentrations of 1. Theoretical, spectroscopic, and diffraction data are used to explain the formation and structures of closely related [Mo2Cp 2(μ-SMe)3(μ-C2HnR] z- complexes (n = 0-4 and z = 0, 1), including 1-3. © 2005 American Chemical Society.

On the basis of single crystal diffraction analyses it is shown that conversion of 13H-dibenzo(a,i)fluoren-13-one into its oxime causes distortion of the aromatic framework because of steric crowding. The oxime is, in consequence, chiral.Key words: oxime, crystal structure, chirality.

The crystal structure of trimethylammonio n-hexadecylsulfonamidate contains antiparallel monolayers stabilized by strong C−H···O bonds (C···O 3.22 A). There are also significant C−H···X (X = N, O) bonds linking adjacent layers. The structure suggests that nitrogen ylides have potential as amphoteric surfactants. The crystallography of paraffinic monolayers is discussed and the crystal structures of n-C16H33X compounds are shown to belong to three distinct types.

The reduction of [Mo2(Cp)2(µ-SMe)3(µ-O)]+ (1+) has been investigated by cyclic voltammetry and controlled-potential electrolysis in THF- and MeCN/NBu4PF6 without added acid or in the presence of various acids HX (HX: HTsO, CF3CO2H, HBF4). Reduction in the presence of acid follows an ECrevE mechanism in which the intermediate chemical step is an acid-base equilibrium between 1 and [Mo2(Cp)2(µ-SMe)3(µ-OH)]+ (2+). This electrochemical process is followed by protonation of the neutral µ-hydroxo complex 2 to afford different products which depend both on the solvent (THF or MeCN) and on the nature of the acid. Controlled-potential electrolysis of 1+ in the presence of HX (2 equiv.) leads to the generation of binding sites and finally gives products identical to those obtained from protonation of 2 by HX. The complex [Mo2(Cp)2(µ-SMe)3(µ-η1,η1-OCOCF3)] (3) which can be obtained either by protonation of 2 by CF3CO2H or by reduction of 1+ in the presence of CF3CO2H, has been characterized crystallographically. In the presence of HBF4 protonation of 1+ gives 22+. The reactivity of 2+ and of the complexes [Mo2(Cp)2(µ-SMe)3(H2O)(TsO)] (4) and [Mo2(cp)2(µ-SMe)3(H2O)L]+ (L = H2O or THF) (6+), all of which contain a terminal aqua ligand, has also been investigated. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

The diynol ester PhC(O)OCH2CC–CCCH2OH readily forms very long (4 cm) needle-shaped crystals. The crystal structure in the range 100–293 K contains strong O–H⋯O hydrogen bonds which link molecules related by the operation of a 21 screw axis into chains which are parallel to the long axis of the needle. Coefficients of linear expansion suggest that attractive intermolecular forces are strongest in the direction of the needle axis.

Pestalotiopsin A is a structurally unique, caryophyllene-type sesquiterpene which has shown immunosuppressive activity and cytotoxicity in preliminary assays. A stereocontrolled approach to the functionalised 2-oxabicyclo[3.2.0]heptane core of pestalotiopsin A is described. This constitutes the first synthetic studies on pestalotiopsin A. Our approach includes a samarium(II)-mediated 4-exo-trig cyclisation and a trans-lactonisation process triggered by the addition of alkylytterbium reagents to a cyclobutanone intermediate. Further manipulation provides access to advanced intermediates which are excellent precursors for the future construction of the final ring of the target.

Crystals of 9-methylfluoren-9-ol, C(14)H(12)O, undergo a reversible phase transition at 176 (2) K. The structure of the high-temperature alpha form at 200 K is compared with that of the low-temperature beta form at 100 K. Both polymorphs crystallize in space group P1 with Z = 4 and contain discrete hydrogen-bonded R(4)(4)(8) ring tetramers arranged around crystallographic inversion centres. The most obvious changes observed on cooling the crystals to below 176 K are an abrupt increase of ca 0.5 A in the shortest lattice translation, and a thermal transition with deltaH = 1 kJ mol(-1).

A series of complexes trans-[PdCl(2)L(2)] has been prepared by the reaction of [PdCl(2)(PhCN)(2)] and/or Na(2)[PdCl(4)] with L = pyridine or quinoline ligands having one or two carboxylic acid groups. These complexes can form 1-D polymers through O-H.O hydrogen bonding between the carboxylic acid groups, as demonstrated by structure determinations of [PdCl(2)(NC(5)H(4)-4-COOH)(2)], [PdCl(2)(NC(5)H(4)-3-COOH)(2)], and [PdCl(2)(2-Ph-NC(9)H(5)-4-COOH)(2)]. In some cases, solvation breaks down the O-H.O hydrogen-bonded structures, as in the structures of [PdCl(2)(NC(5)H(4)-3-COOH)(2)].2DMSO and [PdCl(2)(2-Ph-NC(9)H(5)-4-COOH)(2)].4DMF, while pyridine-2-carboxylic acid underwent deprotonation to give the chelate complex [Pd(NC(5)H(4)-2-C(O)O)(2)]. The complexes trans-[PdCl(2)L(2)], L = pyridine-3,5-dicarboxylic acid or 2,6-dimethyl pyridine-3,5-dicarboxylic acid, self-assembled to give 2-D sheet structures, with hydrogen bonding between the carboxylic acid groups mediated by solvate methanol or water molecules. In the cationic complexes [PdL'(2)L(2)](2+) (L'(2) = Ph(2)PCH(2)PPh(2), Ph(2)P(CH(2))(3)PPh(2); L = pyridine carboxylic acid; anions X(-) = CF(3)SO(3)(-)), hydrogen bonding between the carboxylic acid groups and anions or solvate acetone molecules occurred, and only in one case was a polymeric complex formed by self-assembly.

A highly efficient and stereoselective synthesis of unnatural cyclic sila-substituted β-amino acids has been developed from simple starting materials. The key step is nucleophilic ring opening of an intermediate aziridine with an umpolung synthon for the carboxylate anion. Functional group manipulation and deprotection reactions allow access to the desired trans β-amino acids.

The reactions between alcohols ROH (R = Me, Et) and RR(OH)2 (RR = CH2−CH2) and the [perfluoro(sulfanyl)vinyl]diiron complex [{Fe(CO)3}2{µ-C(SMe)(CF3)CβCαF2}] (1) in THF at room temperature involve substitution at the Cα atom to give new (alkoxymethylene)thiaferracyclobutadiene compounds [{Fe(CO)3}2{µ-S(Me)C(CF3)CβCα(OR)2}] [R = Me (2a), Et (2b); RR = CH2CH2 (2c)]. Treatment of 1 with aniline and (methoxycarbonyl)hydrazine, bases of intermediate strength according to Pearson, produces α,β-substituted thiaferracyclopentadiene [{Fe(CO)3}2{µ-S(Me)C(CF3)Cβ(NHR)Cα(NHR)}] [R = Ph (5a), NHC(O)OMe (5b)] complexes. It is suggested that these compounds form through initial nucleophilic attack at Cα to give the zwitterionic intermediate [{Fe(CO)3}2{µ-S(Me)C(CF3)CC(NRH)2}] (f). Thermally induced C−F bond activation is a feature of these reactions. When 1 reacts with thioamides containing three “hard” competitive primary and secondary amine functions and one “soft” thione function, the nucleophile first attacks at Cα through a secondary amine and, in a second step, at Cβ through the thiol function to give α,β adducts [{Fe(CO)3}2{µ-S(Me)C(CF3)CβSC(=NR2)N(R1)Cα(Cβ−Cα)] [R1 = NH2, R2 = CH3 (6a); R1 = CH3, R2 = H (6b); R1 = R2 = CH3 (6c)] possessing novel iminothiazolidine systems fused to the five-membered metallacyclic ring. Treatment of 1 with acetylhydrazine, which has three “hard” nucleophilic functions, results in the formation of the compound [{Fe(CO)3}2{µ-S(Me)C(CF3)C(H)C(10)NNC(Me)O(C(10)−O)}] (7a), in which an oxadiazole function is fused to the thiaazaferracyclohexene ring. The position of the fluorine substituent on the CαCβCγ(CF3)S(Me) ring of ferracyclopentadiene complexes has been found to be the essential factor determining the specific activation of the C−F bond. A single fluoro substituent attached to the β-carbon atom of the chain can be activated by nucleophiles to give α,β adducts [{Fe(CO)3}2{µ-S(Me)C(CF3)Cβ(X)Cα(NRR′)}] [X = OR′′, R = R′ = R′′ = Me (3a); X = OR′′, R = R′′ = Me, R′′ = C(O)NMe2 (3b); X = SR′′ (4)]. In contrast, complexes in which a single fluorine atom is linked to the α-carbon atom do not undergo C−F bond cleavage reactions. X-ray structures of compounds 2a, 3b, 5a, 5b, 6a and 7a are reported.

The bis(nitrile) compound [Mo2Cp2(µ-SMe)3(MeCN)2](BF4) (1) (Cp = C5H5) reacted with substituted hydrazines RNHNH2 (R = Me, Ph) in acetonitrile at room temperature to give the stable diazene species [Mo2Cp2(µ-SMe)3(μ-η2-HN=NR)](BF4) [R= Me (2), Ph (3)]. Compounds 2 and 3 could be readily deprotonated with BuLi to produce neutral diazenido species [Mo2Cp2(µ-SMe)3(µ-η2-N=NR)] [R = Me (4), Ph (5)]. Photolysis of 4 in THF induced isomerization of the diazenide bridge, affording the complex [Mo2Cp2(µ-SMe)3(µ-η1-N=NMe)] (8). This species underwent protonation at the outer nitrogen atom (Nβ) to give the stable isodiazene/hydrazido(2−) complex [Mo2Cp2(µ-SMe)3(μ-η1-N=NHMe)](BF4) (9) which isomerised slowly back into 2 on warming. The molecular structure of the µ-η2-methyldiazenido complex 4 was established by an X-ray diffraction study.

cited By 9; International audience; The bis(μ-thiolato)dicobalt complex [Co2Cp2(μ-SMe)2] (1) reacts with alkyne-cobalt complexes [Co2(CO)6(μ-F3CCCR)] (2) to give tri- and tetranuclear cobalt cluster compounds. When R=CF3 the main product is [Co2(CO)4(μ-CF3C2CF 3)μ-Co2Cp2(μ-SMe)2] (3) but the trinuclear cluster [Co3Cp(CO)4(μ-SMe)2(μ-CF 3C2CF3)] (4) is also obtained in low yield. When R=H the products are the isomeric clusters [Co3Cp(CO)4(μ-SMe)2(μ-CF 3C2H)] (5 and 6), [Co3Cp2(CO)3(μ-SMe)(μ-CF 3C2CH)] (7) and [CpCo(CO)2]. The solid state structures of 3, 4, 5 and 7 have been established by X-ray analysis. The 50 electron triangular cluster 4 has weak Co-Co bonds [2.573(1), 2.800(1), 2.838(1) Å]. The alkyne ligand bridges the shortest of these bonds in perpendicular fashion. 5 and 7 contain open chain tricobalt units [Co-Co 2.39-2.57 Å] more typical of 50 electron M3 species. In these complexes the alkyne is π-bonded to the central metal atom and σ-bonded to both terminal cobalt atoms. Variable temperature NMR indicates that 5, 6 and 7 each exist in solution as interconverting isomers which differ in the configuration at one sulphur atom. For 5 the activation parameters [ΔH‡=64 kJ mol-1 and ΔS‡=-85 J K-1 mol-1] were obtained spectroscopically. In the solid, molecules of 7 contain an asymmetrically bridging carbonyl [Co-C 1.833(4) and 2.050(3) Å] which is not detectable in the solution spectra. © 2001 Elsevier Science B.V.

The paramagnetic μ-amidato species [Mo2Cp2(μ-MeCONH)(μ-SMe)3]BF42a+ (Cp = η-C5H5) is formed exclusively when the compound [Mo2Cp2(MeCN)2(μ-SMe)3]BF41a in powder form is kept in air, whereas the same starting complex in solution gives a mixture of the μ-amidato species and the μ-oxo complex [Mo2Cp2(μ-O)(μ-SMe)3]BF43. The oxo complex is formed quantitatively on warming [Mo2Cp2(μ-Cl)(μ-SMe)3]BF4 in water. The reduction of 2a+ by NaBH4 in CH3CN affords the molecular product [Mo2Cp2(μ-MeCONH)(μ-SMe)3] 2a which has been characterised by X-ray analysis.

The putative aglycone of pseudopterosin G–J and its enantiomer were synthesised enantiospecifically from 2,3-dimethoxytoluene and η3-allyl cationic complexes of molybdenum and iron respectively. The A→AB→ABC annulation strategy entailed the use of allyl cations or their equivalents for the creation of the three benzylic stereogenic centres. The X-ray structure of tetrahydronaphthalene (−)-41a was determined

The reaction of the perfluorosulfanylvinyldiiron(I) complex [{Fe(CO)3}2{μ-C(SMe)(CF3)Cβ(CαF2)}] (1) with secondary mono- and diamines (L = Me2NH, (CH2)4NH, HN(CH2)4NH) in a 1:1 ratio in dichloromethane at room temperature led in a multistep reaction to the new monoaminocycloferrathiapentadiene compounds [{Fe(CO)3}2{μ-S(Me)C(CF3)CFCX}] (Χ = NMe2 (2), N(CH2)4 (3), N(CH2)4NH (4)) and [[{Fe(CO)3}2{μ-S(Me)C(CF3)CFC]2{μ-N(CH2)4N}] (5). However, when the reaction of 1 was conducted in THF with a large excess of amine, the diaminocycloferrathiabutene complexes [{Fe(CO)3}2{μ-S(Me)C(CF3)C(CX2)}] (X = NMe2 (6), N(CH2)4 (7)) and [{Fe(CO)3}2{μ-S(Me)C(CF3)C(CX)}] (X = MeN(CH2)2NMe (8), HN(CH2)2 NH (9)) were formed. It is suggested that these compounds form via initial nucleophilic attack at Cα to give the common zwitterionic intermediate [{Fe(CO)3}2{μ-S(Me)C(CF3)C(CFNX2)] (C). Thermally induced C−F bond activation is a feature of these reactions. Thermolysis of diaminocycloferrathiabutene compounds (6−9) in tetrahydrof...

γ,δ-Unsaturated aldehydes having a fully substituted centre in either the α- or β-positions, have been prepared from substituted γ-butyrolactones and undergo efficient 4-exo-trig cyclisation on treatment with samarium(II) iodide to give functionalised cyclobutanols. In all cases cyclisation occurs with complete diastereocontrol to give anti-cyclobutanol products. The stereochemistry of the products has been confirmed by NOE and X-ray crystallographic studies. In the cyclisation of substrates having a third substituent on the double bond, α- to the ester, significant control is achieved at the third newly formed stereocentre lying outside the ring. The origin of the stereoselectivity at this third centre and its marked dependence on cosolvent are discussed.

A general modular approach to the members of the pederin family of antitumour agents is exemplified by syntheses of mycalamide B and theopederin D as well as a formal synthesis of pederin. All three compounds are prepared from 6-lithio-2,3-dimethyl-4-phenylselenomethyl-3,4-dihydro-2H-pyran and 2-(3-chloropropyl)-3,3-dimethyl-3,4-dihydro-2H-pyran-4-one.

International audience; [Mo2Cp2(μ-SMe)3(CH3CN) 2](BF4) (1) reacts with H[BF4] in acetonitrile at room temperature to give the tetrakis (acetonitrile) compound [Mo2Cp2(μ-SMe)2(CH3CN) 4](BF4)2 (3) through replacement of one SMe bridge by two terminal CH3CN ligands. In sharp contrast, the carbonyl analogue [Mo2Cp2(μ-SMe)3(CO)2]+ (2) fails to undergo a similar reaction. This suggests that the electronic properties of the ancillary ligands L in the [Mo2Cp2(μ-SMe)3L2]+ moiety govern the activation of a sulfur atom in protonation reactions. An X-ray diffraction study shows that 3 contains two CpMo(CH3CN)2 units bridged by two SMe groups and linked by a long Mo-Mo bond of 3.000(1) Å.

The reaction of [Mo(SC6F5)(CF3CCCF3)2(η5-C5H5)] 1a with MeO2CCCCO2Me at –30 °C gave a butadienyl complex [Mo{η4-C(CF3)C(CF3)C(CO2Me)C(CO2Me)(SC6F5)}(CF3CCCF3)(η5-C5H5)] which has been shown by X-ray analysis to contain an (η5-C5H5)Mo(η2-CF3CCCF3) unit attached to the C(CF3)C(CF3)C(CO2Me)C(CO2Me)SC6F5 butadienyl ligand through a CO2Me carbonyl oxygen atom and Cα, Cγ, and Cδ of the butadiene chain. The structure and bonding in this complex and in related butadienyl and co-ordinated ester complexes are compared. It rearranges above ca. –20 °C to give isomeric complexes [Mo{η5-C(CF3)C(CF3)C(CF3)C(CF3)C(CO2Me)C(CO2Me)SC6F5}(η5-C5H5)] in which linkage of the butadienyl and co-ordinated alkynes has occurred to give η5 or η6 tris- (alkyne) ligands. The complex [W(SC6H4Me-4)(CF3CCCF3)2(η5-C5H5)] 1b and MeO2CCCCO2Me reacted at –20 to –15 °C to give a butadienyl complex [W{η5-C(CF3)C(CF3)C(CO2Me)C(CO2Me)(SC6H4Me-4)}(CF3CCCF3)(η5-C5H5)] similar to the molybdenum complex but containing a co-ordinated thiolate sulfur instead of a carbomethoxy oxygen bonded to the metal. It isomerises above ca. –10 °C to give the sixteen electron complex [W(SC6H4Me-4){η4-C(CF3)C(CF3)C(CO2Me)C(CO2Me)C(CF3)C(CF3)}(η5-C5H5)] containing a novel seven-membered metallacyclic ring. In contrast 1b and non-activated alkynes RCCR′ (R = R′ = Me; R = Me or Ph, R′ = Ph) reacted to give the η3- and η4- butadienyl complexes [W{η3-C(CF3)C(CF3)C(R)C(R′)SC6H4Me-4}(CF3CCCF3)(η5-C5H5)] and [W{η4-C(CF3)C(CF3)C(Me)C(Me)SC6H4Me-4}(CF3CCCF3)(η5-C5H5)] with no evidence for alkyne trimerisation. The pathways which lead to different alkyne oligomerisation patterns are discussed.

The natural herbicide herboxidiene was constructed from two key fragments using a modified Julia olefination based on the benzothiazolyl sulfone activator. Key steps in the synthesis of the C1–C10 oxane fragment were (a) a modified Julia olefination using a 1-phenyl-1H-tetrazolyl sulfone as activator and (b) an intramolecular addition of an alkoxide to an α,β-unsaturated ester. Key steps in the synthesis of the C11–C19 polyketide fragment were (a) a directed aldol reaction using a camphor-10,2-sultam as auxiliary; (b) an Ireland–Claisen rearrangement and (c) a hydroxy-directed epoxidation.

Several new complexes of chiral and achiral tetradentate Schiff bases with copper (II), nickel (II) and oxovanadyl (IV) ions have been synthesised and characterised and the structures of [Cu ( R -salpn) (OH 2 )] and [Cu (±-busalcx)] have been elucidated by X-ray analysis. [Cu ( R -salpn) (OH 2 )] is essentially square pyramidal with an unusually long bond [2.494 (4) A] from Cu to the oxygen of the apical water molecule. Molecules are linked by hydrogen bonding between the coordinated water and the salpn oxygens of neighbouring molecules. A long contact between a salpn CH 2 hydrogen and a neighbouring copper atom [H(3B). . .Cu = 2.966 (1) A] might be regarded as a CH···Cu hydrogen bond and completes a pseudo-octahedral coordination about copper. [Cu (±-busalcx)] displays tetrahedrally-distorted planar coordination about the copper atom and has no significant intermolecular contacts. The copper, nickel and vanadyl complexes were screened as homogeneous catalysts for the oxidation by Bu t OOH or H 2 O 2 of PhMeS to PhMeSO. All of them are active catalysts but of the chiral complexes only [Cu ( R , R -busalcx)] produced a reasonable enantiomeric excess (14%). Supporting the complexes on silica improved the enantioselectivity of the less sterically hindered [Cu ( R -salpn) (OH 2 )] ( from 2 to 10%), but diminished that of the more hindered [Cu ( R , R -busalcx)], probably by slowing the reaction to such an extent that the uncatalysed oxidation could compete effectively. Finally [Cu (salen)], [Cu ( R -salpn)] and [Ni ( R -salpn)] were synthesised in the pores of zeolites X and Y. These were shown to be active heterogeneous catalysts for the sulfide to sulfoxide oxidations, but no significant e.e. resulted from the use of the chiral catalysts.

Three successive reactions of a dimethoxy arene with allylic cation equivalents were used to convert 2,3-dimethoxy-4-methyl-1-iodobenzene to the hexahydro-1H-phenalene system of the potent marine antiinflammatory pseudopterosins G–J.

Triazolidinediones react with each enantiomeric bornanesultam derivative of tiglic acid to produce the appropriate ene adduct in high yield and with excellent regioselectivity and diastereo­selectivity. The optically pure products, viz. N-[(3R)-3-(4-methyl-3,5-dioxo-1,2,4-triazolidin-1-yl)-2-methyl­enebutano­yl]-(1S,2R)-bornane-10,2-sultam 0.15-hydrate, C18H26N4O5S·0.15H2O, and its enantiomer N-[(3S)-3-(4-methyl-3,5-dioxo-1,2,4-triazolidin-1-yl)-2-methyl­enebutano­yl]-(1R,2S)-born­ane-10,2-sultam 0.35-hydrate, C18H26N4O5S·0.35H2O, have been characterized by spectroscopy and single-crystal X-ray analysis. Their structures are the result of Cβ-re attack of the enophile on the double bond of the alkene.

The reaction of either the 84-electron cluster [Pt 6 (μ-CO) 6 (μ-dppm) 3 ] ( 1 ) or the 82-electron cluster [Pt 6 (CO) 6 (μ-dppm) 3 ] 2+ ( 2 ), dppm = Ph 2 PCH 2 PPh 2 , with SnX 3 − or Hg 2 X 2 gave the corresponding bicapped trigonal prismatic 86-electron clusters [Pt 6 ( μ 3 -SnX 3 ) 2 ( μ -CO) 6 ( μ -dppm) 3 ] ( 3 : X = F( 3a , Cl( 3b ), Br( 3e ) or [ Pt 6 (μ 3 - HgX ) 2 (μ- CO ) 6 (μ- dppm ) 3 ] 4 : X = Cl ( 4a ) , Br ( 4b ), l ( 4c ), respectively. The new clusters 3 and 4 have been characterized spectroscopically and 4c has also been characterized by X-ray diffraction. Crystals of 4c·CH 2 Cl 2 ·2Et 2 O are monoclinic, space group P 2 1 c , a=20.092(9), b=18.718(7), c=26.258(7) A , β=108.09(3)° V=9387(6) A 3 , Z =4. The molecular core in 4c is a Pt 6 trigonal prism with each triangular Pt 3 face capped by an Hgl fragment. The intertriangle PtPt bond distances (2.910(1)–2.948(1) A) are longer than the intratriangle PtPt distances (2.634(1)–2.687(1) A) and this is consistent with EHMO calculations. The reaction of 1 with Hg 2 X 2 to give 4 is termed a bicluster oxidative addition; according to predictions from EHMO calculations it should lead to stronger intertriangle PtPt bonding in 3 and 4 than in the precursor cluster 1 , but this is not suppored by structural data observed in 3c and 4c .

Thermal reaction of the chloro-bridged complex [Cp 2 Mo 2 ( μ -Cl)( μ -SMe) 3 ] 1 with the dithiols HS(CH 2 ) n SH ( n = 2 or 3) affords the quadruply thio-bridged complexes [Cp 2 Mo 2 { μ -S(CH 2 ) n SH}( μ -SMe) 3 ] where n = 2 ( 2 ) or 3 ( 3 ). 2 has been shown by X-ray diffraction to contain the μ - η 1 -dithiolate ligand − S(CH 2 ) 2 SH which bridges an Mo-Mo single bond whose length is 2.606(1)A. The substitution reaction of the chloro bridge in 1 also occurs with phenylphosphine, H 2 PPh, giving the μ -phosphido compound [Cp 2 Mo 2 ( μ -HPPh)( μ -SMe) 3 ] 4 . In contrast with diphenylphosphine, HPPh 2 , the thiolate ligand trans to the chloro bridge is replaced by a PPh 2 group, giving the new μ -chloro complex [Cp 2 Mo 2 ( μ -Cl)( μ -PPh 2 )( μ -SMe) 2 5 . All new products have been characterized by spectroscopic analyses.

The crystal structure of the molecular salt [Pt 3 Re(CO) 2 P(OMe) 3 (μ 3 -O) 2 (μ-dppm) 3 ][AsF 6 ], dppm = Ph 2 PCH 2 PPh 2 , has been determined by X-ray diffraction. The crystals are monoclinic, space group P 2 1 / c , a = 15.614(2), b = 21.550(2), c = 24.810(2) A, β = 93.518(10)°, V = 8332.5(13) A 3 , Z = 4, R = 0.0501 for 7403 reflections with I ≥ 2 σ ( I ). The structure of the cation contains a Pt 3 Re(μ 3 -O) 2 core with a tetrahedral arrangement of the metal atoms. One Pt atom is not directly involved in metal-metal bonding, which is limited to a triangle containing one Re and two Pt atoms [Pt-Pt 2.815(1), Pt-Re 2.779(1) and 2.835(1) A]. The packing of ions in the crystal is governed by their relative size: the large cations self-assemble into one-dimensional aggregations, leaving the anions to occupy the cavities in the cationic substructure. Crystal cohesion is enhanced by hydrogen bonding of C-H ⋯ O type, involving carbonyl oxygen atoms, and by C-H ⋯ F interactions.

The reaction of phosphines PXYH (X  Y  Ph, i-Pr; X  Ph, Y  H) or ethanethiol with the perfluorovinyl compound [{Fe(CO)3}2{μ-C(SMe)(CF3)CCF2}] (1) proceeds with cleavage of one CF bond and gives rise to unusual ligand transformations. The multicenter processes involved lead to new diiron complexes [{Fe(CO)3}2{μ-C(SMe)(CF3)C(PXY)CF}] (X  Y  Ph, 2a; X  Y-i-Pr, 2b; X  Ph, Y  H, 2c) and [{Fe(CO)3}2{μ-C(SMe)(CF3)C(SEt)CF}] (3). Mechanisms for these reactions are proposed. The fluxional behavior of 2a and 3 has been investigated by variable-temperature 13C NMR spectroscopy. The molecular structure of 2a has been established by a single-crystal X-ray diffraction study. The Fe2(CO)6 core contains an FeFe bond of 2.633(1)A bridged by the six-electron donor C(SMe)(CF3)C(PPh2)CF ligand. 2a crystallizes in the triclinic space group P 1 with a = 9.019(2), b = 9.550(2), c = 18.583(3) A , α = 101.06(2), β = 92.53(2), γ = 116.48(2)°, R = 0.0419 for 3984 reflections.

The reaction of [ν-C5Me5Mo(CO)3]2 with allyl chloride in refluxing THF gives the mononuclear complex [(ν-C5Me5)MoCl2(ν3-C3H5(CO)] (1). Thermolysis of complex 1 in THF or toluene in presence of dimethyldisulfide affords the unexpected complex [(ν-C5Me5)MoCl]2(μ-Cl)(μ-O)(μ-SMe) (2). Similar reactions are observed with allyl bromide and give the analogous bromide complex 3. X-ray analysis establishes that complex 3 contains a Mo2(μ-Br)(μ-O)(μ-SMe) core and that the C5Me5 ligands are cis with respect to the MoMo axis, as are the terminal Br groups. The formally double MoMo bond is relatively long (2.755(1) A). An approximate plane of symmetry normal to the MoMo bond passes through the bridging O, Br and S donor atoms and relates the two C5Me5MoBr units. Complexes 2 and 3 react with HSMe to afford the μ-oxo-bis(μ-thiolato) products [(ν-C5Me5)MoX]2(μ-O)(μ-SMe)2 (X  Cl (4), Br (5)) and the replacement of the chloride bridge in complex 2 by HSCH2CH2SH leads to [(ν-C5Me5)MoCl]2(μ-O)(μ-SMe)(μ-SCH2CH2SH)] (6).

Undecacarbonyl[4(η5)-cyclopentadienyl]-μ3-(4,4,4-trifluorobutaneheptayl)-tetrairon(3 Fe—Fe), [{Fe(CO)3}3{μ3-CC[Fe(CO)2Cp]C(CF3)}] (Cp is η5-C5H5) contains a triangular {Fe(CO)3}3 core [Fe—Fe distances 2.482 (1), 2.663 (1) and 2.693 (1) A] linked via an unusual C3CF3 bridging unit to an Fe(CO)2Cp group.

Treatment of [PtMe2(bu2bpy)] (bu2bpy = 4,4‘-di-tert-butyl-2,2‘-bipyridine) with B(C6F5)3 in the presence of the ligand L gives, under anhydrous conditions, [PtMeL(bu2bpy)][MeB(C6F5)3] {L = CO (1a), C2H4 (2a), PPh3 (3a)}. Similar reactions performed in the presence of H2O afford [PtMeL(bu2bpy)][HOB(C6F5)3] {L = CO (1b), C2H4 (2b), PPh3 (3b)}. In the absence of L, the treatment of [PtMe2(bu2bpy)] with B(C6F5)3 and H2O gives [Pt{HOB(C6F5)3}Me(bu2bpy)] (4), the first published example of a hydroxytris(pentafluorophenyl)borate complex. All of the complexes are fully characterized by NMR and IR spectroscopy and, in the case of complex 4, by an X-ray analysis which confirms the attachment of the [HOB(C6F5)3]- ligand to the square-planar platinum atom via a Pt−O bond of 2.062(2) A. We propose that, in the presence of water, B(C6F5)3 forms an adduct [H2OB(C6F5)3] (which acts as a strong acid H[HOB(C6F5)3]) and this then protonates a Pt−Me bond of [PtMe2(bu2bpy)] forming CH4 and [PtMe(bu2bpy)]+[HOB(C6F5)3]-. This p...

The title complex, [Ni(C7H3NO4)(C6H5N3)3], has been prepared hydro­thermally. Three neutral monodentate benzotriazole ligands occupy meridional sites about the octa­hedrally coordinated nickel(II) cation. The remaining sites are occupied by the N and two O atoms of a tridentate pyridine-2,6-dicarboxyl­ate dianion.

Photolysis of [Cp 2 Mo 2 (μ-H)(μ-ER)(CO) 4 ] (ER  SMe ( 1 ) or SPh ( 2 )) with MeCCMe gives the μ-vinyl complex [Cp 2 Mo 2 { μ - σ : η 2 -C(CH 3 )CHCH 3 }( μ -ER)(CO) 2 ] (ER  SMe ( 5 ) or SPh ( 6 )) as the major product. Partial oxidation of 5 leads to the oxo compounds [Cp 2 Mo 2 (O) { μ - σ : η 2 -C(CH 3 )CHCH 3 }( μ -SR)(CO] with a low yield. Compound 6 has been structurally characterized by X-ray diffraction. The structure contains μ - σ : η 2 -C(CH 3 )CHCH 3 bridging an MoMo double bond whose length is 2.644(1) A. Chemical deprotonation of [Cp 2 Mo 2 (μ-H)(μ-ER)(CO) 4 ] ( 1 or 2 ) affords the anionic complex [Cp 2 Mo 2 (μ-ER)(CO) 4 ] − (R  SMe ( 8 ) and SPh ( 9 )), which is also obtainable by electrochemical reduction. The fluxional behaviour of 8 and 9 and the mechanism of reduction of 1–4 (ER  S t Bu( 3 ) or SePh( 4 )) are described.

International audience; In [CpMo(SPh)(CO)(CNtBu)2], Cp = η5-C5H5, the Mo atom adopts conventional four-legged piano-stool coordination geometry; a pair of cis CNtBu ligands, together with carbonyl and benzenethiolato groups, make up the base. The Mo-CNtBu bond lengths [2.053 (4) Å trans to S, 2.086 (4) Å trans to CO] show a small but significant difference.

The 54-electron cluster cation [Pt3{ReO3}(μ-dppm)3]+, 2, dppm = Ph2PCH2PPh2, reacts with CO, P(OMe)3, Hg, and Tl(acac), acac = MeCOCHCOMe, by addition at the Pt3 center to give the 56-electron cluster cations [Pt3{ReO3}(μ3-L)(μ-dppm)3]+, L = CO (3), Hg (6), or Tl(acac) (5), or [Pt3{ReO3}(L)(μ-dppm)3]+ (4) L = P(OMe)3. Oxidation of 6 in the presence of mercury and NH4[ReO4] gives the bis(mercury) cluster [Pt3(μ3-Hg)2(μ-dppm)3][ReO4]2, 7. The structures of 2[PF6] [cubic, space group Pa3, a = 24.495(1) A, V = 14 697(1) A3, Z = 8, R = 0.0421 for 3113 reflections with I > 2σ(I)], 6[PF6]·2Me2CO [triclinic, space group P1, a = 14.502(5) A, b = 16.712(7) A, c = 20.814(6) A, α = 70.00(3)°, β = 82.52(1)°, γ = 82.39(3)°, V = 4679(3) A3, Z = 2, R = 0.0688 for 7227 reflections with I > 2σ(I)], and 7[ReO4]2·1.5Me2CO [triclinic, space group P1, a = 16.088(5) A, b = 16.307(7) A, c = 19.390(7) A, α = 99.49(2)°, β = 93.70(1)°, γ = 117.30(2)°, V = 4401(4) A3, Z = 2, R = 0.1010 for 7931 reflections with I > 2σ(I)] have be...

The η2-C,C vinyl complexes [M{η3-C(CF3)C(CF3)SR}(CF3CCCF3)(η5-C5H5)]1(M = Mo, R = Pri; M = W, R = Me, Et or Pri) reacted with dimethyl acetylenedicarboxylate R′CCR′(R′= CO2Me) to give products of alkyne trimerisation containing two different oligomerisation sequences depending on whether R′CCR′ occupies a terminal or central position in the alkyne trimer chain, i.e. C(CF3)C(CF3)C(CF3)C(CF3)C(R′)C(R′) and C(CF3)C(CF3)C(R′)C(R′)C(CF3)C(CF3). With M = Mo, kinetic 19F NMR studies established a reaction sequence proceeding above ca.–30 °C via two different butadienyl complexes [M{η2-C(CF3)C(CF3)C(R′)C(R′)SPri}(CF3CCCF3)(η5-C5H5)]2 and 3 to give isomeric trienyl derivatives [Mo{η6-C(CF3)C(CF3)C(CF3)C(CF3)C(R′)C(R′)SPri}(η5-C5H5)]4 and [Mo{η5-C(CF3)C(CF3)C(CF3)C(CF3)C(R′)SPriC(R′)}(η5-C5H5)]5 which were isolated at room temperature. X-Ray diffraction studies established that in each case the trienyl ligand is bound to the metal via an η2-C,C alkenyl linkage, and two σ carbon–metal bonds. In 4 this is accompanied by co-ordination of a CO unit of a carbomethoxy carbonyl whereas in 5 the thiolate sulfur is bonded to the metal. Above room temperature 5 isomerises to give species 6 and ultimately 7 which appears to result from thiolate transfer to the metal to give a seven-membered metallacycle. With M = W, the reactions also proceed via a butadienyl complex 2 but this isomerises via two other intermediates to give trienyl products [W{η6-C(CF3)C(CF3)C(R′)C(R′)C(CF3)C(CF3)SR}(η5-C5H5)] and [WF{η5-C(CF2)C(CF3)C(R′)C(R′)C(CF3)C(CF3)SR}(η5-C5H5)]. X-Ray diffraction studies established that the trienyl ligand in the former is co-ordinated via one σ, two π alkene linkages and a thiolate sulfur. Two isomeric forms were structurally characterised which differ only in the orientation of the thiolate isopropyl substituent which can adopt syn or anti positions. In the fluoride a CF3 fluorine has been transferred to the metal and this has generated a hexatrienyl attachment via a quasi π-allylic interaction and through W–C and W–S σ bonds.

The Diels−Alder reactions of 1,3-diphenylisobenzofuran with acryloylferrocene (1), 4-ferrocenyl-3-buten-2-one (2), cinnamoylferrocene (3), 3-ferrocenyl-1-phenyl-2-propenone (4), chalcone (5), 1-((η6-phenyl)tricarbonylchromio)-3-phenyl-2-propenone (6), 1-phenyl-3-((η6-phenyl)tricarbonylchromio)-2-propenone (7), and (2-nitrovinyl)ferrocene (8) were examined under various conditions. The best results were achieved using SiO2 and a very acidic montmorillonite clay, KSF, as the catalyst, and the reactions were carried out without solvent. Reasonable to good yields of the Diels−Alder (D-A) products were isolated in most cases. X-ray structural studies showed that the adducts 13b and 13h, derived from the (E)-alkenes 2 and 8, have exo-acetyl or -nitro substituents and endo-ferrocenyl groups with respect to the bridging oxygen atom of the 7-oxabicycloheptane ring system. The product 13a from the monosubstituted enone 1 also has an exo-acyl (ferrocenylcarbonyl) group. Aluminum chloride was found to be a good catal...

In the title compound, hexa-micro-chloro-dichlorotetrakis(N-trimethylammonio-p-toluenesulfonamidate-kappa(2)N,O)tetramercury(II), [Hg[Me(3)N(+)N(-)SO(2)C(6)H(4)CH(3)-p]Cl(2)](4) or [Hg(4)Cl(8)(C(10)H(16)N(2)O(2)S)(4)], four nearly linear and parallel Cl-Hg-Cl units associate through pairwise Hg.Cl interactions of 3.1-3.2 A. Each Hg atom is also coordinated through N and O atoms to a ylide molecule. The available structural data indicate that coordination of a sulfonyl-stabilized nitrogen ylide to a metal atom (Hg or Ag) has no detectable effect on its geometry.

The crystal and molecular structure of Ph3SnCH2CH2SC6H4Me-p has been determined by X-ray crystallography. In each of the two independent molecules in the asymmetric unit the tin atom has an irregular tetrahedral geometry, with C−Sn−C valency angles ranging from 104.1(5) to 114.7(5)° in molecule (1) and from 104.6 to 112.7(6)° in molecule (2). The bond lengths, Calkyl−Sn are 2.18(1) and 2.17(2)A (in molecules (1) and (2), respectively) while the Caryl−Sn bond lengths range from 2.11(1) to 2.13(1)A in molecule (1) and from 2.09(1) to 2.14(1)A in molecule (2). The Sn−C−C−S torsion angle, 172(1)° is the same for both molecules. NMR spectral data are presented; the1H NMR spectrum in solution of the central-CH2−CH2-unit suggests that each of the protons on each of the CH2 groups is magnetically distinct and that rotations about the C−C bond are slow on the NMR time scale. Comparisons with similar molecules are made and conformations discussed in terms of steric effects.

The terdentate ligands C6H3-2,6-(CH(2)PCy(2))(2) (PCP: Cy = cyclohexyl) in the octahedral solvento complexes trans-[RhCl2(MeOH)(PCP)] and trans-[RhCl2(EtOH)(PCP)] adopt conformations which minimise the interactions between the sterically demanding Cy groups and the trans chlorides. Comparison of these structures with those of related molecules, including square-pyramidal and square-planar species, suggests an explanation for the different structural types obtained as products from reactions of RhCl3.3H(2)O and various ligands C6H4-1,3-(CH(2)ER(2))(2) with E = N or P.

The synthesis of a number of dimanganese complexes each containing two different bridging phosphido ligands is reported. The complex Mn2(μ-PPh2)(μ-PPhH)(CO)8 (1) is prepared by the reaction of [Mn2(CO)10] firstly with PPh2H followed by reaction with PPhH2 in decalin. The reaction of 1 with CCl4 gives Mn2(μ-PPh2)(μ-PPhCl)(CO)8 (2) and deprotonation of 1 with n-BuLi followed by reaction of the deprotonated species with RX (X  halide) or [Mn(CO)5 Br] gives the complexes [Mn2(μ-PPh2)(μ-PPhR)(CO)8 (R  Me(3a),Et(3b , CH2COMe(3c) or CO2Et(3d) and [Mn(μ-PPh2){μ-PPhMn(CO)5}(CO5(CO)8] (4). The deprotonation of [Mn2(μ-PPhH)2(Co)8] with one equivalent of n-BuLi and subsequent reaction with McCOCI gives [Mn2(μ-PPhH)(μ-PPhCOMe)(CO)8] (5) which exists in solution as a mixture of isomers. The structures of [Mn2(μ-PPh2){μ-PPhMn(CO)5}(CO)8] (4) and of trans-Mn2(μ-PPhH)(μ-PPhCOMe)(CO)8] (5) have been determined by single-crystal X-ray studies. All the complexes have been characterized spectroscopically and by elemental analysis.

The reaction between C6H4-1,3-(CH2PCy2)2, Cy = cyclohexyl, and RhCl3·3H2O produced trans-[RhCl2(OH2) {C6H3-2,6-(CH2PCy2)2}], [RhCl2(OH2)(PCP)]. The product was characterised spectroscopically and the crystal and molecular structure of its 2-propanol solvate, [RhCl2(OH2)(PCP)·propan-2-ol, C35H61Cl2O2P2Rh, as determined by X-ray analysis. The crystals are monoclinic, space group P21/a, with A = 11.513(1), B = 25.874(2), C = 13.576(1) i.., β = 113.47(6)°, V = 3709.7(3) i..3, M = 749.71, Z = 4. Comparisons with other rhodium-aqua complexes show that the Rh---O distances are extremely sensitive to trans influence, but sensitive to other factors such as the oxidation state or coordination number of the metal ion, or steric crowding. The charge on the complexes appears to exert only a minor influence.

The synthesis of trans -[NiBr{C 6 H 3 -2,6-(CH 2 PCy 2 ) 2 }], Cy = cyclohexyl, and its characterisation by spectroscopy and single crystal X-ray analysis are described. The constraints imposed by the bulky terdentate ligand lead only to minor distortions of the square planar nickel(II) coordination (PNiP = 161.6(1)°). The nickel coordination is compared with those found in related complexes with terdentate N- and P-donor ligands.