Late Transition Metal Compounds with 1,1′‐Bis(phosphino)ferrocene Ligands

Abstract

Abstract:The syntheses of several new zinc compounds with 1,1′-bis(phosphino)ferrocene ligands and their phosphine chalcogenide derivatives are reported. The X-ray crystal structures

Protic Ferrocenyl Acyclic Diamino Carbene Gold(I) Complexes

“…presumably forming a bridging chlorido ligand (Supporting Information, Figures S12-S13). [60] Structure Determination Single crystals of 2 Et2 and 2 iPr2 suitable for X-ray diffraction analyses were obtained by recrystallization from THF/petroleum ether. While both complexes display the expected linear coordination at the gold(I) ion, a syn conformation and unremarkable bond lengths and angles around the gold and ferrocene units (Supporting Information, Table S1), the packing in the crystalline state strongly differs (Figure 1).…”

“…However, [2 Et2 ] + and [2 iPr2 ] + further react on the time scale of hours after chemical oxidation (Figure 2). Several possibilities can be suggested, namely deprotonation at the amine after oxidation of the ferrocene, [82,83] slow electron transfer from gold(I) to iron(III) [41] followed by dimerization of the gold(II) radical, [84,85] formation of gold(III) via disproportionation or chlorine radical/Cl 2 formation followed by oxidative addition, [86][87][88][89] or chloride loss from gold(I) [60] followed by chloride attack on iron(III) of the multifunctional open-shell complexes [2 Et2 ] + and [2 iPr2 ] + .…”

Triple the fun: tris(ferrocenyl)arene-based gold(i) complexes for redox-switchable catalysis

“…Furthermore, we wanted to ascertain the integrity of the oxidised species, since Nataro and co-workers observed loss of a chlorido ligand (G, Chart 2) from dinuclear gold(I) complexes based on 1,1 0bis(phosphanyl)ferrocenes aer chemical oxidation using tris(pbromophenyl)ammoniumyl tetrakis(pentauorophenyl)-borate ("Magic Blue"). 131 While the group of Peris found oxidationinduced protonation (H, Chart 2) of the ferrocenylimidazolylidene backbone in their gold(I) chloride complexes upon addition of acetylferrocenium tetrauoroborate, 126 Heinze and co-workers described valence isomerisation from, initially, Fe III /Au I to Fe II /Au II (J, Chart 2) assisted by both the SbCl 6…”

Transition-metal complexes of group 12 with 1,1′-bis(phosphanyl)ferrocene ligands

“…9). The P-Zn-P bite angle is larger than the corresponding angle of the dppf and dppr [1,1 0 -bis(diphenylphosphanyl)ruthenocene] analogues (Butler et al, 1985;Nataro et al, 2003), but shorter than zinc complexes of dppdtbpf and dippf [1,1 0 -bis(diisopropylphosphanyl)ferrocene] derivatives (Yeo et al, 1999;Hartlaub et al, 2017). This difference can be attributed to the steric hindrance of the bulky cyclohexyl groups (de Lima et al, 1995).…”

“…Due to their poor basicity, the most readily available and attractive diarylphosphanyl substrates cannot be monooxidized in this way. Our interest in studying transition-metal compounds containing 1,1 0 -bis-(phosphanyl)ferrocene ligands of transition metals in groups 11 and 12 has emerged from the discovery that little has been defined in respect of the structural forms of their complexes with simple salts, particularly zinc and cadmium (Hartlaub et al, 2017). Herein we report the first highly efficient and convenient method for the selective catalytic monooxidation of 1-diphenylphosphanyl-1 0 -(di-tert-butylphosphanyl)ferrocene (dppdtbpf) and its coordination behaviour towards cadmium(II) chloride.…”