Structure of hexafluorotetrapyridine dimolybdenum(III)

Kiriazis, L.; Mattes, R.; Obst, Frank

doi:10.1016/s0020-1693(00)86805-x

Cited by 4 publications

(4 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…234 Reaction of molybdenum or tungsten hydrides with HBF 4 has also led to some fluoro complexes, [W(PMe 3 ) 4 H 2 F 2 ], [W(PMe 3 ) 4 H 2 F(HF 2 )], [Mo(PMe 3 ) 4 H 2 F(HF 2 )], [{MoH 2 (PMe 2 Ph) 3 } 2 -(m-F) 3 ][BF 4 ] and [W(PMe 3 ) 4 H 2 F 2 (H 2 O)]. 235-239 Other fluoro-species include a rare example with a thioether ligand, [MoF(S)([16]aneS 4 )]-[BF 4 ], 240 [{Mo(MeCN) 4 O} 2 (m-F)][BF 4 ] 2 , 241 [MoOF(RNC) 4 ][BF 4 ], 242 and [Mo 2 F 6 (py) 4 ] 243.…”

mentioning

confidence: 99%

Medium and high oxidation state metal/non-metal fluoride and oxide–fluoride complexes with neutral donor ligands

2013

View full text Add to dashboard Cite

While most high and medium oxidation state (O.S. ≥ 3) metal and non-metal fluorides and oxide fluorides are strong Lewis acids, exploration of their coordination chemistry with neutral ligands has been limited and mostly non-systematic. This is despite the very different properties conferred on the acceptor centre by the small electronegative fluoride ligands compared to the heavier halides. This article sets out these key differences, discusses possible synthetic routes, the key characterisation techniques, and appropriate bonding models. Current knowledge of the coordination chemistry of d, f and p-block fluorides and oxide fluorides with neutral ligands (with donor atoms drawn from Groups 15 and 16 and including N-heterocyclic carbenes) is then presented and discussed, and the differences in properties compared to complexes containing the heavier halides are illustrated. The emphasis is on work published post 1990, but earlier work is also included as essential background and where no more recent information exists. Attention is drawn to unexplored areas meriting investigation and to possible applications of these complexes.

show abstract

mentioning

confidence: 99%

Medium and high oxidation state metal/non-metal fluoride and oxide–fluoride complexes with neutral donor ligands

2013

View full text Add to dashboard Cite

show abstract

“…Similar coordination motifs have been previously observed for [Zr 2 F 12 ] 4– in [Co((NH 2 ) 2 C 2 H 4 ) 3 ] 2 [Zr 2 F 12 ][SiF 6 ]·4H 2 O and for [MF 4 (OS(CH 3 ) 2 ) 2 ] 2 (M = Zr, Hf). , Although the Mo–Mo distance [exptl 3.4981(3); calcd 3.518 Å] is much smaller than the sum of the van der Waals radii [ R vdW (Mo) = 2.1 Å], the bond angles of the four-membered ring [F b –Mo–F b , exptl 65.21(5)°, calcd 65.2°; Mo–F b –Mo, exptl 114.79(5)°, calcd 114.8°], the low Wiberg bond index (WBI = 0.01), and the negligible (3.3 kJ mol –1 ) donor–acceptor interaction, as determined by second-order perturbation theory of the natural bond orbital (NBO) analysis, collectively indicate that no significant bonding character is present between the Mo centers. Conversely, an appreciably smaller Mo–Mo distance [2.533(1) Å] is observed in the octahedral Mo III complex [MoF 3 (NC 5 H 5 ) 2 ] 2 , which thus contains a substantial bonding interaction . MoF 5 (NC 5 H 5 ) 2 , [MoF 5 (NC 5 H 5 )] 2 , and MoOF 4 (NC 5 H 5 ) 2 represent the first neutral adducts of MoF 5 and the first heptacoordinate adduct of MoOF 4 , respectively, to be conclusively characterized.…”

Section: Resultsmentioning

confidence: 99%

Lewis Acid Behavior of MoF₅ and MoOF₄: Syntheses and Characterization of MoF₅(NCCH₃), MoF₅(NC₅H₅)_n, and MoOF₄(NC₅H₅)_n (n = 1, 2)

et al. 2021

View full text Add to dashboard Cite

The Lewis acid−base adducts MoF 5 (NC 5 H 5 ) n and MoOF 4 (NC 5 H 5 ) n (n = 1, 2) were synthesized from the reactions of MoF 5 and MoOF 4 with C 5 H 5 N and structurally characterized by X-ray crystallography. Whereas the crystal structures of MoF 5 (NC 5 H 5 ) 2 and MoOF 4 (NC 5 H 5 ) 2 are isomorphous containing pentagonal-bipyramidal molecules, the fluorido-bridged, heptacoordinate [MoF 5 (NC 5 H 5 )] 2 dimer differs starkly from monomeric, hexacoordinate MoOF 4 (NC 5 -H 5 ). For the weaker Lewis base CH 3 CN, only the 1:1 adduct, MoF 5 (NCCH 3 ), could be isolated. All adducts were characterized by Raman spectroscopy in conjunction with vibrational frequency calculations. Multinuclear NMR spectroscopy revealed an unprecedented isomerism of MoOF 4 (NC 5 H 5 ) 2 in solution, with the pyridyl ligands occupying adjacent or nonadjacent positions in the equatorial plane of the pentagonal bipyramid. Paramagnetic MoF 5 (NC 5 H 5 ) 2 was characterized by electron paramagnetic resonance (EPR) spectroscopy as a dispersion in solid adamantane as well as in a diamagnetic host lattice of MoOF 4 (NC 5 H 5 ) 2 ; EPR parameters were computed using ZORA with the BPW91 functional using relativistic all-electron wave functions for Mo and simulated using EasySpin. Density functional theory calculations (B3LYP) and natural bond orbital analyses were conducted to elucidate the distinctive bonding and structural properties of all adducts reported herein and explore fundamental differences observed in the Lewis acid behavior of MoF 5 and MoOF 4 .

show abstract

“…13 In 2, the Re−Re′ bond distance (2.2575(2) Å) is ∼0.02 Å shorter than in Re 2 (ArNCHNAr) 4 Cl 2 (Ar = CH 3 C 6 H 5 (2.2759(3) Å), 7 p-OMe (2.2777(3) Å), m-OMe (2.2765(6) Å), 3,4-Cl 2 (2.2783(4) Å), 3,5-Cl 2 (2.2734(3) Å)). 13 The Re−Re distance of Re 2 (dpf) 4 F 2 (2) is longer than in Re 2 (hpp) 4 F 2 (1), and this elongation is well reflected by a stronger interaction of the axial fluoride ligand (Table 1). The Re−F ax bond length (i.e., 2.059(1) Å) is ∼0.1 Å shorter than in 1.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…The metal–metal bond chemistry of group 6–8 transition-metal complexes containing fluoride ligands is poorly developed, and only six complexes have been reported: Mo 2 F 6 (py) 4 , Mo 2 F 4 (PMe 3 ) 4 , ( n- Bu 4 N) 2 [Re 2 F 8 ], Re 2 (hpp) 4 F 2 , [Re 2 (hpp) 4 F](TFPB) 2 , and Ru 2 (ap) 4 F . One reason is the lack of availability of metal–metal bonded fluoro precursors which can be easily obtained in high yield.…”

Section: Introductionmentioning

confidence: 99%

Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes

et al. 2017

View full text Add to dashboard Cite

Quadruply bonded rhenium(III) dimers with the stoichiometry ReLF (1, L = hexahydro-2H-pyrimido[1,2a]pyrimidinate (hpp); 2, L = diphenyl formamidinate (dpf)) were prepared from the solid-state melt reactions (SSMRs) between (NH)[ReF]·2HO and HL. Those compounds were characterized in the solid state by single-crystal X-ray diffraction and in solution by UV-visible spectroscopy and cyclic voltammetry. The compound [Re(hpp)F]PF (3) was prepared from the one-electron oxidation of Re(hpp)F with [CpFe]PF. Compounds 1-3 are isostructural with the corresponding chloro derivatives. In solution, compound 1 undergoes two one-electron oxidations. Comparison with its higher halogen homologues reveals that Re(hpp)F (1) is more easily oxidized than its chloro and bromo analogues.

show abstract

Structure of hexafluorotetrapyridine dimolybdenum(III)

Cited by 4 publications

References 10 publications

Medium and high oxidation state metal/non-metal fluoride and oxide–fluoride complexes with neutral donor ligands

Medium and high oxidation state metal/non-metal fluoride and oxide–fluoride complexes with neutral donor ligands

Lewis Acid Behavior of MoF₅ and MoOF₄: Syntheses and Characterization of MoF₅(NCCH₃), MoF₅(NC₅H₅)_n, and MoOF₄(NC₅H₅)_n (n = 1, 2)

Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes

Contact Info

Product

Resources

About

Structure of hexafluorotetrapyridine dimolybdenum(III)

Cited by 4 publications

References 10 publications

Medium and high oxidation state metal/non-metal fluoride and oxide–fluoride complexes with neutral donor ligands

Medium and high oxidation state metal/non-metal fluoride and oxide–fluoride complexes with neutral donor ligands

Lewis Acid Behavior of MoF5 and MoOF4: Syntheses and Characterization of MoF5(NCCH3), MoF5(NC5H5)n, and MoOF4(NC5H5)n (n = 1, 2)

Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes

Contact Info

Product

Resources

About

Lewis Acid Behavior of MoF₅ and MoOF₄: Syntheses and Characterization of MoF₅(NCCH₃), MoF₅(NC₅H₅)_n, and MoOF₄(NC₅H₅)_n (n = 1, 2)