Mono-condensed product of ferrocenylformyl acetone with ethylenediamine and its complexes of lanthanide chlorides

Two substrates, three products: Reactions between ferrocene-carboxaldehyde and dioxaphospholene, characterization and crystal structures of oxygenated C3- and C4-chain-containing ferrocenes

“…However, contrary to what is observed with benzaldehyde or its substituted derivatives [14,16], treatment of ferrocenecarboxaldehyde with the biacetyl-trimethylphosphite adduct followed by methanolysis does not provide the expected symmetrically 3-substituted acac, FcCH(C(O)CH 3 ) 2 . Instead, the -diketone product 1-ferrocenyl-1,2-propanedione (1, Fc-C(O)C(O)CH 3 ) was formed, and when slight modifications of Ramirez" experimental conditions were applied, two new C 4 side-chain containing ferrocenyl complexes, 4-methoxy-4-ferrocenyl-3-hydroxy-3-methyl-2-butanone (2,…”

“…β-diketones RC(=O)CH(R")C(=O)R"", that can be functionalized in the three sites of the molecule, are attractive building blocks for the construction of polydentate Schiff bases, and both the parent derivative 2,4-pentanedione (R = R"" = CH 3 , R" = H) and its organometallic counterpart ferrocenoylacetone (R = Fc, R" = H, R"" = CH 3 ) have been widely employed to prepare Schiff base half-units (Fc =( 5 -C 5 H 5 )Fe( 5 -C 5 H 4 )) [1][2][3][4]. Monocondensation of such organic or organometallic β-diketones with an appended O, N or S donor group containing primary amine leads to the formation of tridentate Schiff bases, also called "half unit", through the imine and amine nitrogen atoms and the carbonyl oxygen [1].…”

“…The thermal ellipsoids are drawn at the 40% probability level. Selected bond distances (Å) and angles (°): C(10)-C(11) 1.452(3), C(11)-O(12) 1.227(2), C(11)-C(13) 1.545(3), C(13)-O(15) 1.203(2), C(13)-C(14)1.484(3), avg Fe(1)-C(C 5 H 5 ) = 2.0531(19), avg Fe(1)-C(C 5 H 4 ) = 2.0504(19); C(10)-C(11)-O(12) 124.28(17), O(12)-C(11)-C(13) 117.74(17), C(11)-C(13)-O(15) 119.95(17), O(15)-C(13)-C(14) 123.79(19). Within complex 1 the fragment C(10)-C(11)-O(12) is almost coplanar with the substituted cyclopentadienyl ring with a dihedral angle of 13.1°, as typically observed in other structurally characterized ferrocenylarylglyoxal derivatives [22] and in the symmetrical 1,2diferrocenylethanedione [22b].…”

Synthesis and Electrochemical Behavior of Ferrocenyl β‐Ketoamines FcC(O)CH=C(NH(C6H4‐4‐R‘))R

“…However β ‐ketoamines of type FcC(O)CH=C(NHR)Fc (Fc=Fe( η 5 ‐C 5 H 4 )( η 5 ‐C 5 H 5 ) have not been reported so far. Furthermore, the study of electron‐transfer and electronic interactions within ferrocenyl substituted β ‐ketoamines has mainly been neglected [1,18] and generally refers to β ‐ketoamine metal complexes [10a–f,18b,c,19] …”

Molecular and Solid State Structure of the Doubly-Substituted B-Diketone 3,3'-Bis(ferrocenylmethyl)pentane-2,4-Dione#

“…7,8 On the other hand, β-diketones are attractive building blocks for the construction of polydentate Schiff bases, and both the parent derivative 2,4-pentanedione (CH 3 COCH 2 COCH 3 ), [9][10][11][12] and its organometallic counterpart ferrocenoylacetone (FcCOCH 2 COCH 3 , 13 Fc = (h 5 -C 5 H 5 )Fe(h 5 -C 5 H 4 )) have been widely employed to prepare tridentate Schiff base complexes, also called half-units, upon mono-condensation with primary diamines. [14][15][16][17][18][19][20][21][22] In pursuit of our research work aimed at extending the scope of acyclic Schiff base metalloligands, [14][15][16][17] we decided to synthetize new β-diketones functionalized at the central carbon of the 1,3-dione system, using cerium(IV) ammonium nitrate (CAN), a versatile reagent in a variety of synthetic transformations through oxidation of organic molecules, [23][24][25] as catalyst in the carbon-carbon bond formation between ferrocenyl alcohol substrates and 1,3-diketones.…”