Gas-phase formation of mono- and dications from iron-subgroup decamethylmetallocenes and their calculation by the density functional method

Cationic and neutral transition metal complexes with a tetramethylfulvene or trimethylallyldiene ligand

“…95 The calculated Os7CH 2 bond length in the [CpOs{C 5 Me 3 (CH 2 ) 2 }] 2+ complex is 2.33 # A. 99 The M7C (11) and M7C(1) bond lengths and the tilt angles a in 18-electron singly and doubly charged cationic Z 6 -C 5 Me 4 CH 2 and Z 7 -C 5 Me 3 (CH 2 ) 2 complexes of Group 8 metals calculated using the density functional theory (DFT) 100 are listed in Table 12. It can be seen that the calculated M7C (11) bond lengths tend to increase on passing from Z 6 -complexes to Z 7 -complexes.…”

Synthesis, structures and reactions of some metallocene alcohols

“…Structures were solved using SIR I R92 [46], with additional nonhydrogen atoms being located, where necessary, from difference Fourier maps. Full-matrix least square refinements were carried out against F (on all data for 8 and 9; on data with I > 2rðIÞ for (10)(11)(12) using CRYS-R YS -TALS TALS [47]. Chebychev polynomial weighting schemes (five-term for 8; three-term for (9)(10)(11)(12) were applied [48].…”

“…Full-matrix least square refinements were carried out against F (on all data for 8 and 9; on data with I > 2rðIÞ for (10)(11)(12) using CRYS-R YS -TALS TALS [47]. Chebychev polynomial weighting schemes (five-term for 8; three-term for (9)(10)(11)(12) were applied [48]. Details of the data acquisition and refinements are summarised in Table 1; complete crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre, CCDC 210126-210130 for compound 8-12. In the structure of 9 the half-molecule containing the atom Fe(2) was modelled with a disordered tert-butyl group [C(32), C(34) and C(36) with 33% occupancy; C(33), C(35) and C(37) 67% occupancy].…”

“…Many have been synthesised as precursors to metallocenestablised carbocations, which can be described as (g 5 -cyclopentadienyl-g 6 -fulvene)metal(II) and whose structures and bonding have been extensively studied [1][2][3][4][5][6][7][8][9][10][11][12], and which have themselves served as synthetic intermediates [12][13][14][15][16][17]. Metallocenyl alcohols have also been used as intermediates in the synthesis of chiral ligands for asymmetric catalysis [18,19].…”

Enantiomeric-Enriched Ferrocenes: Synthesis, Chiral Resolution, and Mathematic Evaluation of CD-chiral Selector Energies with Ferrocene-Conjugates

“…Such primary, secondary, and tertiary Fc-carbocations as solids were firstly synthesized and characterized by NMR [ 50 ] and later X-ray analysis data for permethylated ferrocene carbocation, and (C 5 Me 5 )Fe(C 5 Me 4 )C + H 2 was reported [ 51 ]. Moreover, the density-functional method was used for ab initio calculations of the geometry and total energy of (C 5 Me 5 )Fe(C 5 Me 4 )CH 2 -cation [ 52 ]. Chiral FcC + HR are known and have been extensively used to access various chiral ferrocene derivatives [ 25 , 27 ].…”