Electrochemical investigations on phospha ferrocenes

Synthesis and Properties of [CoCp*(2,5‐PC4tBu2H2)]: The First Monophosphacobaltocene

“…The seminal early Fenske–Hall theoretical treatment of phosphaferrocenes63 gave a monophosphaferrocene LUMO with a′ symmetry and a total ligand contribution of about 32 %; this may be compared with the a″ SOMO showing 33 % ligand character that is found for the phosphacobaltocene by ADF. Cyclic voltammetry data for phosphaferrocenes43–46, 64 suggest, broadly, that the reversibility of the phosphaferrocene reduction wave falls as the number of phosphorus atoms rises, and Winter and Geiger have recently provided evidence that the pentaphosphaferrocenide radical anion [Cp*FeP 5 ] − ( 14 ) undergoes rapid dimerisation through two ring phosphorus atoms 65. Given the comparatively poor π‐acceptor properties of the monophospholyl ligand with respect to its polyphospholyl analogues,60 the stability of these 19 VE monophosphametallocene derivatives with respect to the corresponding polyphosphametallocenes seems likely to reflect a lesser ligand participation in the SOMO.…”

Lithiation and alkylation reactions of the tri-phosphaferrocenes, [Fe(η5-P3C2tBu2)(η5-C5R5)], (R=H and Me): Crystal and molecular structures of the LiFe(η4-P2C2tBu2PnBu)(η5-C5Me5)2 dimer, [Fe(η4-P2C2tBu2PnBuMe)(η5-C5Me5)] and cis-[PtCl2(PMe3)Fe(η4-P2C2tBu2PnBuMe)(η5-C5H5)]

“…The nature of the bonding in phosphaferrocenes and related phosphametallocenes containing the g 5 -ligated 3,5-ditertiarybutyl-1,2,4-triphospholyl ring system, has been explored by electrochemical measurements in solution and gas-phase photoelectron spectroscopic techniques, coupled with supportive DFT calculations [12,21,22]. These studies have established that replacement of CR fragments by P in the corresponding parent metallocene reduces the overall electron density at the metal centre.…”

Synthesis and structural characterisation of lanthanide and actinide phosphaorganometallic complexes derived from the 3,5-di-tert-butyl-1,2,4-triphospholyl ring anion, P3C2But−2: Crystal and molecular structures of [M(η5-P3C2But2)2(η2-P3C2But2)] (M=Sc, Y, Tm, and U)

“…a (Å) 11.066 (2) 11.062 (2) 11.0942 (6) 11.0720(3) b (Å) 16.014 (2) ber of the central metal atom. The use of cyclopentadienyl ligands with bulky substituents such as (1,3-(TMS)C 5 H 3 ) has facilitated the isolation and characterisation of monomeric tris(cyclopentadienyl) complexes of cerium, samarium and thorium [36][37][38].…”

“…Sc [3], Ti [4,5], V [6], Cr [17], Mn [18], Fe [7][8][9][10][11][12][13], Co [19], Ni [21][22][23][24][25], Ru [13][14][15][16], and Rh [16,20]) and main group elements (e.g. Ga [26], In [27][28][29], Tl [26], Sr [30], and Pb [31]).…”