The chemistry of the carbon–transition metal double and triple bond: annual survey covering the year 2002

Herndon, James W.

doi:10.1016/j.cct.2003.11.001

Cited by 58 publications

(6 citation statements)

References 637 publications

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“…These molecules often owe their existence to coordination to the metal centers which stabilize them sufficiently for characterization. The allenylidene complexes have been studied less than the C 1 and C 2 homologues, although the literature has been extensively reviewed over recent years with annual surveys, [17][18][19][20][21][22] allenylidenes and higher cumulenylidenes reviewed in detail, 23,24 polymetallic C n systems, 25 C 3-5 ruthenium cumulenylidenes, 26 iridium cumulenylidenes, 27 and rhodium allenylidenes 28 being the most relevant. The seminal contributions of Selegue 29 and Berke 30 provided the first examples and, in the case of the former, a general route to these compounds.…”

Section: Introductionmentioning

confidence: 99%

Coordinating Tectons: Bipyridyl Terminated Allenylidene Complexes

et al. 2008

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A series of complexes with π-conjugated carbon chains terminated by bipyridyl moieties has been prepared. These allenylidene complexes were derived from 9-hydroxy-9-ethynyl-4,5-diazafluorene, the preparation of which is reported; the new allenylidene complexes are highly colored with the cumulated carbon chain terminating in a bipyridyl unit providing a site for further coordination. The synthesis, characterization, and X-ray structure determination of trans-[MCl(P∩P) 2 dCdCd(4,5-diazafluoren-9-yl)]PF 6 (M ) Ru, P∩P ) bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,2-bis(dimethylphosphino)ethane (dmpe); M ) Os, P∩P ) dppm) are described. The effect of the variation in metal and ligand on electronic and electrochemical characteristics of these complexes has been investigated by using UV-vis, solution electrochemistry, and a combination of these techniques in spectroelectrochemical experiments. DFT calculations have been performed on trans-[RuCl(P∩P) 2 dCdCd(4,5-diazafluoren-9-yl)] q (P∩P ) dppm, bis(dimethylphosphino)methane (dmpm); q ) -1, 0, +1, +2) and subsequently solvent-corrected calculations with use of COSMO were also undertaken to examine the nature of electronic transitions in various oxidation states.

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Section: Introductionmentioning

confidence: 99%

Coordinating Tectons: Bipyridyl Terminated Allenylidene Complexes

et al. 2008

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“…Vinylidene complexes of various metals also function as strategic intermediates for the catalytic conversion of alkynes such as cycloaromatization of conjugated enediynes, the dimerization of terminal alkynes, and the addition of oxygen, nitrogen, and carbon nucleophiles to alkynes . Therefore the synthesis and reactivity of these unsaturated ligands, particularly the ruthenium vinylidene system, are nevertheless under active investigation . While the reactivity of mononuclear vinylidene complexes finds their applications, studies on dinuclear metal complexes with highly unsaturated carbon-rich ligands such as acetylide, vinylidene, and allenylidene have focused more or less on the electron-transfer phenomena mediated by a conjugated bridging ligand …”

Section: Introductionmentioning

confidence: 99%

Preparation of Dinuclear Vinylidene Complexes and Their New Deprotonation Reactions

et al. 2007

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The dinuclear dicationic vinylidene complex {[Ru]dCdC(Ph)CH 2 C(CH 2 CN)dCd[Ru]} 2+ (7a, [Ru] ) Cp(PEt 3 ) 2 Ru) is prepared from the reaction of ICH 2 CN with {[Ru]dCdC(Ph)CH 2 CtC[Ru]} + (6a). Deprotonation of 7a by n-Bu 4 NOH is followed by a cyclization process yielding the stable complex 9a, containing a five-membered carbocyclic ring ligand, which is fully characterized by 2D-NMR analysis and a single-crystal X-ray diffraction analysis. Similarly deprotonation of {[Ru]dCdC(Ph)CH 2 C(CH 2 -COOEt)dCd[Ru]} 2+ (8a) gave the stable product 11a containing a bridging ligand also with a similar five-membered carbocyclic ring. The cyclization process is affected by an ancillary ligand on the Ru metal center. Thus the analogous dinuclear complex 9b, with a bistriphenylphosphine ligand on one metal, which is prepared in a similar manner from] ) Cp(PPh 3 ) 2 Ru), is unstable, undergoing isomerization to give the dinuclear complex 10b, containing a cyclopropenyl ligand.

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“…Electron-donating as well as electron-withdrawing substituents in the β-phenyl ring were tolerated, such that lithiated 1b − d reacted with 3c and 3g to give 4i − k . The relative configuration of compounds 4a − k was established by 2D-NOESY correlations and confirmed by the X-ray analysis in the case of 4g . It is worth pointing out that, in contrast with 1a-Li , ortho-lithiated cis -stilbene oxide, when treated with 3g , gave an inseparable mixture of several products, whatever the experimental conditions in terms of temperature, reaction time, and lithiating agent ( n -BuLi, s -BuLi, PhLi).…”

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confidence: 54%