Metal complexes of heteroarenes. 5. Bis(.eta.6-phosphorin)metal coordination: is there conformational preference?

Geometry and electronic structure of Vn(Bz)m complexes

“…Judai et al 15 from photoelectron spectra experiments concluded that V(Bz) 2 has a negative electron affinity. An electrochemical study by Elschenbroich et al 16,17 also resulted in a negative EA for V(Bz) 2 . A previous theoretical study, based on Hartree-Fock calculations preformed by Judai et al predicted a negative EA value ͑Ϫ1.99 eV͒ for the V(Bz) 2 complex.…”

Phosphaalkene, phospholyl and phosphinine ligands: New tools in coordination chemistry and catalysis

“…Note that chromium 171, molybdenum 172, tungsten 173 [167] and iron(0) 174 [168] complexes of C 5 H 5 P were also prepared and structurally characterized as well as the homoleptic Rh(I) complex 175 of the 2-methyl-3,6-diphenylphosphinine (Figure 35) [169]. The 17 VE [V(η 6 -C 5 H 5 P) 2 ] vanadium(0) complex 176 was also successfully synthesized through the metal atom-ligand condensation technique [170]. Contrary to what observed with groups 6-10 complexes coordination occurs through the π-system of the ring to yield the sandwich complex.…”

Bonding situation and stability of η1- and η6-bonded heteroarene complexes M(η1-EC5H5)6 and M(η6-EC5H5)2 (M=Cr, Mo, W; E=N, P, As, Sb, Bi)

“…The group-6 metals chromium and molybdenum which are in the middle of the transition metals rows are particularly interesting because they exhibit a diverse binding mode with heteroarene ligands. Both coordination modes are experimentally observed for group-6 metals chromium [8][9][10][11] and molybdenum [12][13][14]. So far, for tungsten only g 1 -complexes with phosphinine and arsenine are experimentally verified [12,15].…”

“…The coordination chemistry of this class of ligands has systematically been investigated in experimental studies of Elschenbroich [5][6][7][8][9][10][11][12][13] with the focus on the preparation of neutral compounds. The results show that the phosphinine ligand prefers the g 6 -binding mode in complexes with early metals of the first transition metal row while in complexes of late transition metals g 1 coordination via the lone pair is favored [5][6][7].…”