Direct Evidence for O−H···NC Hydrogen Bonding in a Cyanide-Bridged Lanthanide−Transition-Metal Complex (H₂O)₆(DMF)₆Ho₂[Ni(CN)₄]₃:  An Eight-Coordinated Holmium Center with a Bicapped (Square Face) Trigonal Prismatic Geometry

Abstract

The lanthanide-transition-metal complex (H 2 O) 6 (DMF) 6 Ho 2 [Ni(CN) 4 ] 3 , 1, was prepared from the reaction of Ho(NO 3 ) 3 ‚6.5H 2 O with K 2 [Ni(CN) 4 ] at a 2:3 molar ratio in DMF (DMF ) N, N-dimethylformamide). This compound is a model compound for studying the effects of H 2 O ligands on the coordination geometry of lanthanide centers and the tendency to form oligomers rather than extended arrays with cyanide bridges. The presence of multiple hydrate water molecules appears to inhibit the formation of an extended array complex containing cyanide bridges but favors intermolecular hydrogen bonds between oligomers. The Ho centers are trans-bridged through a [Ni(CN) 4 ] 2-unit. Each Ho center also forms an isocyanide linkage with a terminal [Ni(CN) 4 ] 2-unit. Holmium is eight-coordinated. It is bound to three DMF molecules and three H 2 O molecules in addition to two [Ni(CN) 4 ] 2-units. The coordination geometry of Ho is a distorted bicapped (square face) trigonal prism. The X-ray crystal structure and IR spectra support the presence of strong-to-moderate O-H‚‚‚NC hydrogen bonds. Crystal data for 1: monoclinic space group P2 1 /n, a ) 8.907(1) Å, b ) 25.579(1) Å, c ) 11.761(1) Å, ) 105.138(1)°, Z ) 2.

A Novel Cyanide-Bridged Thulium-Nickel Heterobimetallic Polymeric Complex {(H2O)2(DMF)10Tm2[Ni(CN)4]2}[Ni(CN)4] including O-H…N Hydrogen Bond

“…8 Here we describe detail of the synthesis and crystal structure of a novel cyanide-bridged thulium(III) nickel heterobimetallic polymeric complex {(H 2 O) 2 (DMF) 10 4 2− complex which serves as a link between two extended chains by hydrogen bond.…”

Two Novel 5f–3d Bimetallic Cyano‐Bridged Complexes

“…[1] Du et al [2] have listed another 15 applications. Although there have been several reports of 3d-5f complexes, [3] attention has not been directed towards cyano-bridged 3d-5f complexes, so that we decided to synthesize such complexes comprising the uranyl ion, because the electronic structure and spectroscopy of this actinide ion are well-documented.…”

“…Although there have been several reports of 3d-5f complexes, [3] attention has not been directed towards cyano-bridged 3d-5f complexes, so that we decided to synthesize such complexes comprising the uranyl ion, because the electronic structure and spectroscopy of this actinide ion are well-documented. [4] Two novel complexes involving also the coordination of dimethylformamide (dmf) and aqua ligands to U VI are reported herein: [UO 2 (H 2 O) 4 -(dmf) 2 ] 0.5 ·{UO 2 [M(CN) 6 ](dmf) 2 }, M = Co (1), Fe (2) and their spectroscopic properties have been investigated.…”

Synthesis and X-ray crystal structure of cationic polynuclear hydroxide acetylacetonate lanthanide(III) clusters with homodinuclear or heterodinuclear decacarbonyl hydrides: [HMo2(CO)10]− and [HCrW(CO)10]−

“…Recently, heteronuclear compounds, obtained by reaction of lanthanide complexes with transition metal carbonyls, were used in selective catalytic processes [11].…”