Syntheses and molecular structures of Ru3(μ-H)(μ3-CPh2CCCCPh)(CO)9 and Ru3{μ3-CPhCHCC(CPh2)CHCPh}(μ-CO)(CO)8

Bruce, Michael I.; Meier, Andrew C.; Skelton, Brian W.; White, Allan H.; Zaitseva, Natasha N.

doi:10.1016/j.jorganchem.2003.12.031

Cited by 2 publications

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“…The dehydration of propargylic alcohols (alkynols), HC⋮CCRR‘(OH), by transition metals was discovered by Selegue in 1982, providing a general method for the synthesis of compounds containing cumulenic chains such as allenylidene complexes (MCCCRR‘), although the first allenylidene complex was synthesized in a different way by Fischer and Berke . The chemistry of the allenylidene complexes has attracted a great deal of interest, − various factors, such as (i) the significance of complexes with such an unsaturated carbon chain as potential precursors for molecular wires or polymers in the field of new materials with optoelectronics properties (namely liquid crystals and species with nonlinear optical properties), ,,,− …”

Section: Introductionmentioning

confidence: 99%

Allenylidene Iron(II) Complexes and Their Deprotonation, Nucleophilic Addition Reactions, and Cathodic Protonation toward Alkynyl Derivatives: A Chemical and Electrochemical Study

et al. 2005

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The allenylidene complexes trans- [FeBr(dCdCdCRR′) (depe) 2 ][Y] (R ) Me, R′ ) Ph, 1; R ) R′ ) Ph, 2; R ) R′ ) Et, 3; depe ) Et 2 PCH 2 CH 2 PEt 2 ; Y ) BF 4 , BPh 4 ) were obtained by reaction of trans-[FeBr 2 (depe) 2 ] with the appropriate alkynol HCtCCRR′(OH), in MeOH and in the presence of Na[BF 4 ] or Na[BPh 4 ]. Deprotonation of 3 or nucleophilic γ-addition to 2 led to the neutral enynyl and alkynyl complexes trans- [FeBr{-CtCC(dCHMe)Et}-, in acetonitrile solution, upon reaction with NHMe 2 , NH 2 Me, and PMe 3 , respectively. The complexes have been characterized by multinuclear NMR and IR spectroscopy, FAB-MS, and elemental analysis and, in the cases of 5a and 6a, also by X-ray diffraction analysis. Controlled-potential electrolysis of 2 yields the alkynyl species trans-[FeBr{-CtCCPh 2 (H)}(depe) 2 ] (8) via a 2e -/H + process, and the oxidation potential of the complexes, measured by cyclic voltammetry, has allowed us to estimate the electrochemical Pickett (P L ) and Lever (E L ) ligand parameters for the cumulenic ligands. These are then ordered (together with related ligands) according to their net π-electron acceptor minus σ-donor ability as follows: carbynes > aminocarbyne > CO > vinylidenes > aryl allenylidene > alkyl allenylidene > NCR . phosphonium alkynyl > cyanoalkynyl, Br -, NCO -> alkynyl, enynyl, aminoalkynyl.

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