Some reactions of azides with diynyl-bis(phosphine)ruthenium-cyclopentadienyl complexes

Abstract not availableMichael I. Bruce, Alexandre Burgun, Jonathan George, Brian K. Nicholson, Christian R. Parker, Brian W. Skelton, Nancy Scoleri, Christopher J. Sumby, Natasha N. Zaitsev

Lithiation of diynyl-ruthenium complexes: routes to novel metallated functional diynes

Conditions for the efficient lithiation of the diynyl group in complexes Ru(CCCCH)(PP)Cp′ [(PP)Cp′ = (dppe)Cp (*) 1, (PPh 3)2Cp 2 have been investigated. Addition of two equiv. LiBu to the diynyl complexes in thf solution at -78°C effects rapid conversion to putative Ru(CCCCLi)(PP)Cp′. Assays using subsequent reactions with either SiClMe3 or AuCl(PPh3) indicate that up to 80% conversion can be achieved. Reactions of the lithiated species with organic electrophiles [MeI, MeC(O)Cl, PhC(O)Cl, ClC(O)OMe, PhCHO, Ph 2CO and metal-containing substrates [MClPh3 (M = Ge, Sn), trans-RhCl(CO)(PPh3)2, cis-PtCl2(PPh 3)2, CuCl(PPh3), (AuCl)2(μ-dppm) proceed to give functionalised diynyl complexes or bimetallic derivatives which are accessible only with difficulty or not at all from the parent diynes. Single-crystal X-ray diffraction molecular structures of Ru(CCCCR)(dppe)Cp (*) (R = Me, GePh3) are reported: there is significantly greater delocalisation along the Ru-C4-R chain in the GePh 3 derivative. © 2011 Elsevier B.V. All rights reserved.Michael I. Bruce, Nancy Scoleri, Brian W. Skelto

Syntheses and molecular structures of some polyfluoroaryldiynyl-ruthenium complexes

Lithiated Ru(C{triple bond, long}CC{triple bond, long}CH)(dppe)Cp* reacts with polyfluoroaromatic compounds C6F5X (X = F, OMe, CN, NO2) and C10F8 to give novel polyfluoroaryldiynyls end-capped with the Ru(dppe)Cp* group. Addition of tcne to Ru(C{triple bond, long}CC{triple bond, long}CC6F5)(dppe)Cp* afforded the butadienynyl Ru{C{triple bond, long}CC[{double bond, long}C(CN)2]C(C6F5){double bond, long}C(CN)2}(dppe)Cp*, while protonation with HBF4·OEt2 resulted in cycloaddition to give [1,3-{Cp*(dppe)RuC{triple bond, long}C}2{μ-C4H(C6F5)2}]BF4. XRD molecular structures of complexes with X = F, CN, OMe and the C10F7 derivative are reported. © 2010 Elsevier B.V. All rights reserved.Michael I. Bruce, Nancy Scoleri, Brian W. Skelton, Allan H. Whit

Some chemistry of trans-Ru(C triple bar CC triple bar CH)(2)(dppe)(2): Syntheses of bi- and tri-metallic derivatives and cycloaddition of tcne

Conventional reactions of trans-Ru(CCCCH) 2(dppe) 2 1 with RuCl(PP)Cp′ or AuCl(PPh 3) have given the complexes trans-Ru(CCCCR)(CCCCR′)(dppe) 2 [R = H, Ru(PP)Cp′, Au(PPh 3); R′ = Ru(PP)Cp′, (PP)Cp′ = (PPh 3) 2Cp, (dppe)Cp, (dppe)Cp (not all combinations)]. The Au(PPh 3) derivatives react with Co(μ 3-CBr)(μ-dppm) (CO) 7 to give trans-Ru(CCCCH){CCCCC[Co 3(μ-dppm)(CO) 7]}(dppe) 2 and trans-Ru{CCCCC[Co 3(μ-dppm) (CO) 7]} 2(dppe) 2, which contain respectively four- and five-carbon and two five-carbon chains linking the metal centres. Also described is the addition of tcne to trans-Ru(CCCCH) 2(dppe) 2 to give the bis(η 1-tetracyanobutadienyl) complex trans-Ru{CCC[C(CN) 2]CHC(CN) 2} 2(dppe) 2 11, of which the single crystal X-ray structure is reported. © 2011 Elsevier B.V. All rights reserved.Michael I. Bruce, Susanne Büschel, Marcus L. Cole, Nancy Scoleri, Brian W. Skelton, Allan H. White, Natasha N. Zaitsev

Some cyclic ligands obtained from reactions of polycyanocarbon-metal complexes

Dedicated to our friend and colleague Claude Lapinte on his 65th birthday, in recognition of his extensive contributions to organo-iron chemistry.Abstract not availableMichael I. Bruce, Alexandre Burgun, Martyn Jevric, Jonathan C. Morris, Brian K. Nicholson, Christian R. Parker, Nancy Scoleri, Brian W. Skelton, Natasha N. Zaitsev

Alkynyl and poly-ynyl derivatives of carbon-tricobalt clusters

A series of alkynyl-tricobalt carbonyl clusters, Co3(μ3-CnR)(μ-dppm)(CO)7 [R = But, Ph, C6H4I, C6H4CCPh, SiMe3, Fc, Au(PPh3)] containing three, five or seven carbons in the chain, have been prepared by elimination of phosphine–gold(I) halides in reactions between Co3(μ3-CBr)(μ-dppm)(CO)7 and Au(CCR)(PPh3) or between Co3{μ3-CCCAu(PR3)} (μ-dppm)(CO)7 (R = Ph, tol) and ICCR′ (R′ = SiMe3, Fc). The use of poly-substituted arenes or ferrocenes has enabled preparation of the complexes 1,4-{(OC)7(μ-dppm)Co3 (μ3-CCC)}2C6H3X-5 (X = H, Br), 1,3,5-{(OC)7(μ-dppm)Co3(μ3-CCC)}3C6H3 and 1,1′-{(OC)7(μ-dppm)Co3 (μ3-CCC)}2Fc′ [Fc′ = Fe(η-C5H4-)2]. The X-ray determined molecular structures of 12 of the complexes are reported.Alla B. Antonova, Michael I. Bruce, Paul A. Humphrey, Maryka Gaudio, Brian K. Nicholson, Nancy Scoleri, Brian W. Skelton, Allan H. Whited and Natasha N. Zaitsevahttp://www.elsevier.com/wps/find/journaldescription.cws_home/504090/description#descriptio

Validation of the albumin-indocyanine green evaluation model in patients with resected hepatocellular carcinoma and comparison with the albumin-bilirubin score

Background The albumin-indocyanine green evaluation (ALICE) model based on serum albumin and indocyanine retention rate has been shown to be an effective method for predicting postoperative outcomes in hepatocellular carcinoma patients. Aim of the study was to validate the ALICE model in a large Western cohort of patients by comparing the albumin-bilirubin (ALBI) score and Child-Turcotte-Pugh (CTP) score. Methods A total of 400 patients who underwent hepatic resection from January 2005 to June 2016 at three centers were enrolled. The ALICE, ALBI, and CTP scores were computed for all patients. Results The ALICE score correlated better with ALBI (r = 0.428) than with CTP score (r = 0.302). Both the ALICE (grade 1: 49%; grade 2: 51%) and the ALBI (grade 1: 52.5%; grade 2: 47.5%) scores stratified the CTP class A patients into two distinct classes. The incidence of ascites (grades 1-3: ALICE 11%, 20%, 58%; ALBI 11%, 23%, 50%) and severe liver failure (ALICE 8.7%, 10.5%, 41.7%; ALBI 8.6%, 12%, 50%) increased with increasing ALBI and ALICE grade and were similar for the same grade. Conclusions The ALICE model can assess hepatic functional reserve and predict postoperative outcomes with efficacy comparable with the ALBI grade and better than the CTP score

Extending Metal-Capped Polyynediyl Molecular Wires by Insertion of Inorganic Metal Units

Several symmetric and asymmetric bis­(metalla-diynediyl)­ruthenium­(II) complexes of the general formula <i>trans</i>-{L_<i>x</i>Ru}­CCCC­{Ru­(dppe)₂}­CCCC­{RuL′_<i>y</i>} (L_<i>x</i>, L′_<i>y</i> = (PPh₃)₂Cp, (dppe)­Cp, (dppe)­Cp*), containing Ru­(dppe)₂ as the central linking group, have been successfully synthesized and characterized spectroscopically. DFT calculations show that their HOMO’s are delocalized over the Ru–C₄–Ru–C₄–Ru chain, suggesting that there is electronic interaction between the terminal RuL_<i>x</i> groups through the C₄ chains and the Ru­(dppe)₂ center. Limited electrochemical measurements reveal that the complexes undergo a series of five stepwise reversible or quasi-reversible oxidation processes

Syntheses and structures of some complexes containing M3(μ-dppm)3 moieties (M = Cu, Ag) linking C4M′Lx groups [M′Lx = Re(CO)3(But 2-bpy), Ru(dppe)Cp∗]

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