1997
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Abstract: The first chalcogen-bridged [1]ferrocenophanes Fe(η-C5H3R)2E (6, E = S, R = H; 7, E = Se, R = H; 12, E = S, R = Me) have been synthesized and characterized both structurally and spectroscopically. Synthesis of sulfur- and selenium-bridged species 6 and 7 was achieved by the reaction of dilithioferrocene·TMEDA (TMEDA = tetramethylethylenediamine) with bis(phenylsulfonyl) sulfide S(O2SPh)2 and selenium diethyldithiocarbamate Se(S2CNEt2)2, respectively, in 20−30% yields. Structural characterization of both 6 and … Show more

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“…Tilting affects the lowest-energy transition in two ways. [24] As the tilt angle increases, the a 1 ' HOMO is raised in energy while the LUMO energy is lowered, which leads to the red shift to lower energy (see Figure 8). Additionally, as tilting reduces the symmetry of the complex (ferrocene is of D 5d (staggered) or D 5h (eclipsed) symmetry while an ansa metallocene can at most have C 2v symmetry) and ligand contributions to the LUMO appear to increase, [15b] the Laporte selection rule is relaxed resulting in a more intense absorption.…”
Section: Electronic Structure and Strain Energies Of Ring-tiltedmentioning
“…[124] Sulfur-and selenium-bridged [1]ferrocenophanes 33 and 34 can be made by typical salt metathesis methods by using dilithiofer- rocene, given careful workup at low temperatures. [24,124] These tilted, strained species should exhibit interesting reactivity but, to date, this area has not been explored in detail.…”
Section: Group 16 Elements As Bridges Sulfur and Seleniummentioning
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“…[60] [Fe(h 5 -C 5 H 4 ) 2 P(p-C 6 H 4 -tBu)] 26.9(3) [61] [Fe(h 5 -C 5 H 4 ) 2 P(Ph)·BH 3 ] 24.38(10) [62] [Fe(h 5 -C 5 H 4 ) 2 P(Ph)·BCl 3 ] 25.01(4) [62] [a] Attachment of the sterically demanding SiMe 3 substituents to the Cp rings introduces further strain, as in the case of the SiMe 2 SiMe 2 bridge. [31] [Fe(h 5 -C 5 H 4 ) 2 Se] 26.4(2) [32] [Fe(h 5 -C 5 H 4 ) 2 S] 31.05(10) [33] [ [a] [35] [Fe(h 5 -C 5 H 3 tBu) 2 SiPh 2 ] 18.81 [36] [(h 5 -C 5 H 4 )Fe(h 5 -C 5 Me 4 )CH 2 S] 18.5(1) [35] [a] Two independent molecules in the unit cell. [b] The largest value in the literature.…”
mentioning
“…However, polyferrocenylethylenes 9 (M ϭ Fe, E ϭ EЈ ϭ CH 2 , RЈ ϭ Me) with a CH 2 OCH 2 spacer (and other polymers derived from the ROP of [2]ferrocenophanes) possess much weaker metal-metal interactions than PFSs, whereas for polyferrocenylsulfides 7 (E ϭ S) the interaction is stronger. 27,37 Polyferrocenylphosphines (PFPs) 7 (E ϭ PR) offer additional possibilities because facile coordination of transition metals to phosphorus is possible. distribution is broad (PDI ϭ ca.…”
Section: Properties Of Ring-opened Polyferrocenes: Pfssmentioning