128247-54-1Relevant articles and documents
Heterobi- and heterotrimetallic transition metal complexes with carbon-rich bridging units
Packheiser, Rico,Walfort, Bernhard,Lang, Heinrich
, p. 4579 - 4587 (2008/10/09)
The syntheses of heterobi- and heterotrimetallic complexes based on (2,2′-bipyridine-5-ylethynyl)-ferrocene (3) are described. Complex 3 is accessible by the Pd(II)/Cu(I)-catalyzed Sonogashira cross-coupling of FcC≡CH (1) (Fc = (η5-C5H4) (η5-C5H5)Fe) with 5-bromo-2,2′- bipyridine (2). The complexation behavior of 3 was investigated. Treatment of 3 with (nbd)Mo(CO)4 (4a) (nbd = norbornadiene) at 25 °C, or refluxing 3 with Mn(CO)5Br (4b), (Me2S) 2PtCl2 (4c), and Ru(bipy)2Cl 2·2H2O (4d) (bipy = 2,2′-bipyridine), respectively, gave the respective heterobimetallic complexes FcC≡C-bipy(MLn) (5: MLn = Mo(CO)4, 6: MLn = Mn(CO)3Br, 7: MLn = PtCl2, 8: MLn = [Ru(bipy)2](PF6)2). Heterotrimetallic FcC≡C-bipy{[Pt(μ-σ,π-C≡CSiMe 3)2]CuFBF3} (12) can be obtained by the subsequent reaction of 7 with Me3SiC≡CH (9) and [Cu(N≡CMe)4]BF4 (11), while [FcC≡C-bipy{[Ti] (μ-σ,π-C≡CSiMe3)2}M]X (14a: M = Cu, X = PF6; 14b: M = Ag, X = ClO4; [Ti] = (η5- C5H4SiMe3)2Ti) were formed by combining 3 with {[Ti](μ-σ,π-C≡CSiMe3) 2}MX (13a: MX = Cu(N≡CMe)PF6,13b: MX = AgOClO 3). The identity of 3,10, and 14a was confirmed by single-crystal X-ray structural studies. The main characteristic features of 3 and 10 are the almost eclipsed conformation of the ferrocene cyclopentadienyl rings, the linear CCp-C≡C-Cbipy moieties, and the coplanarity of both the pyridine and the C5H4 rings. The latter structural motif allows an optimal overlap between the π-orbitals of the cyclopentadienyl, ethynyl, and pyridyl rings. However, in 14a the bipy ligand is tilted by 96.9° toward the η5-C5H4 unit, which most likely is attributable to cell-packing effects. The platinum atom in 10 is held in a somewhat distorted square-planar surrounding. The chelated copper(I) ion in 14a possesses a pseudotetrahedral coordination geometry. Mononuclear 3 exhibits redox peaks in its cyclic voltammogram (E 0 = 0.10 V, ΔEP = 194 mV) for the Fe 2+/Fe3+ redox couple of the Fc unit and for the bipy ligand (E0.1 = -2.36 V, ΔEp = 200 mV; E 0.2 = -2.76 V, ΔEp = 430 mV). Compounds 10, 12, 14a, and 14b additionally show electrode potentials attributed to the respective MLn building blocks.
Monomere Kupfer(I)-Alkyle mit β-Wasserstoffatomen und Kupfer(I)-Aryle mit kondensierten Aromaten; die Festkoerperstruktur von [(η5-C5H4SiMe3)2Ti(CCSiMe3)2]CunC4H9
Stein, Thomas,Lang, Heinrich
, p. 142 - 149 (2007/10/03)
The synthesis of heterobimetallic titanium(IV)-copper(I) complexes of type {[Ti](CCSiMe3)2}CuR {3a, R=iC3H7; 3b, R=nC4H9; 3c, R=cC5H9; 3d, R=9-C13H9; 5a, R=1-C10H7; 5b, R=9-C14H9; [Ti]=(η5-C5H4SiMe3)2Ti} in which monomeric low-valent copper(I) organyls (CuR) are stabilised by the chelating effect of the organometallic ?-tweezer [Ti](CCSiMe3)2 are accessible by the reaction of {[Ti](CCSiMe3)2}CuSC6H4CH2NMe2-2 (1) with equimolar amounts of ER (E=Li, BrMg). These species feature monomeric copper alkyls or aryls, bearing -hydrogen atoms (complexes 3a-3c) or condensed aromatic ?-systems (complexes 5a and 5b). While 3a-3d, 5a and 5b are stable at low temperature in the solid-state, it appeared that in solution 3a-3c undergo β-hydride elimination, affording propene (3a), 1-butene (3b) or cyclopentene (3c). Next to these species, HSiMe3 (8) along with the dimeric titanium-copper acetylide {[Ti](CCSiMe3)(CuCC)}2 (6) is also formed. In contrast, 5b decomposes on heating (30 deg C) to afford the tweezer molecule [Ti](CCSiMe3)2 (9) and (C14H9)2 (10). Possible reaction mechanism for the latter reactions will be discussed. The solid-state structure of 3b is reported. Complex 3b crystallizes in the triclinic space group P1 with cell parameters a=13.659(2), b=17.270(3), c=18.106(4) Angstroem, α=107.64(3), β=100.11(3), γ=108.51(3) deg, Z=4 and V=3681(1) Angstroem3. The most striking structural feature of 3b, which will be discussed, is that the nC4H9 moiety is orientated out of the Ti(CCSi)2Cu plane.
