Electronic structure and spectroscopy of the cycloheptatrienyl molybdenum halide complexes [MoBrL2(η-C7H7)]+ (L2= 2CO, n= 0; L2= 2,2′-bipyridyl, n= 0 or 1)

Roberts, Kathryn A.E.; Brown, Nicholas J. L.; Roberts, Hannah N.; McDouall, Joseph J. W.; Low, Paul J.; Whiteley, Mark W.

doi:10.1016/j.poly.2014.05.027

Cited by 3 publications

(2 citation statements)

References 46 publications

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“…The high intensity transition spectra in experimental (theoretical calculation) were at 240 (260) and 225 (228) nm for PTCTCP and PTCCP, respectively, which describes important absorption properties of both compounds. For PTCTCP, the experimentally observed absorption at 240 nm arises from excitations of HOMO-2 to LUMO, whereas, for PTCCP, the 225 nm wavelength is associated with the ascent from HOMO-1/HOMO to LUMO/ LUMO+1 43 . Figure 3.…”

Section: Uv/visible Spectramentioning

confidence: 96%

New Phosphorus Compounds K[pcl3(x)] (X= Scn, Cn): Preparation and DFT and Spectroscopic Studies

Lashgari

Ghamami

Salgado-Morán

et al. 2016

J. Chil. Chem. Soc.

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Two new phosphorus complexes, potassium trichlorothiocyanophosphate (III) (PTCTCP; K[PCl 3 (SCN)]) and potassium trichlorocyanophosphate (III) (PTCCP; K[PCl 3 (CN)]) were synthesized from the reaction of KSCN and KCN, respectively, with PCl 3 . The chemical formulas and compositions of these compounds were determined by elemental analysis and spectroscopic methods, such as phosphorus-31 nuclear magnetic resonance (NMR) spectroscopy ( 31 P-NMR), Fourier transform infrared (FTIR) spectroscopy, ultraviolet-visible (UV-Vis) spectroscopy and mass spectrophotometry. All of the theoretical calculations and determinations of the properties of these compounds were performed as part of the Amsterdam Density Functional (ADF) program. Excitation energies were assessed using time-dependent perturbation density functional theory (TD-DFT). In addition, the molecular geometry was optimized and the frequencies and excitation energies were calculated using standard Slater-type orbital (STO) basis sets with triple-zeta quality double plus polarization functions (TZ2P) for all of the atoms. The assignment of the principal transitions and total densities of state (TDOS) for orbital analysis were performed using the GaussSum 2.2 program.

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Section: Uv/visible Spectramentioning

confidence: 96%

New Phosphorus Compounds K[pcl3(x)] (X= Scn, Cn): Preparation and DFT and Spectroscopic Studies

Lashgari

Ghamami

Salgado-Morán

et al. 2016

J. Chil. Chem. Soc.

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“…24 Moreover, oxidation state discrepancies exist for several half-sandwich 1,3,5-cycloheptatriene Mo complexes. 25 We previously hypothesized that pentadentate coordination of donor-substituted bis(imino)pyridine (or pyridine diimine, PDI) chelates might allow for the preparation of complexes and catalysts that are not isolable when employing a set of monodentate ligands. 26 Since 2014, we have extended this methodology to study the Mo coordination chemistry of the diphenylphosphinopropyl-substituted PDI chelate, Ph2PPr PDI.…”

Section: Introductionmentioning

confidence: 99%

Isolation of a bis(imino)pyridine molybdenum(i) iodide complex through controlled reduction and interconversion of its reaction products

et al. 2016

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Analysis of previously reported [((Ph2PPr)PDI)MoI][I] by cyclic voltammetry revealed a reversible wave at -1.20 V vs. Fc(+/0), corresponding to the Mo(ii)/Mo(i) redox couple. Reduction of [((Ph2PPr)PDI)MoI][I] using stoichiometric K/naphthalene resulted in ligand deprotonation rather than reduction to yield a Mo(ii) monoiodide complex featuring a Mo-C bond to the α-position of one imine substituent, (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoI. Successful isolation of the inner-sphere Mo(i) monoiodide complex, ((Ph2PPr)PDI)MoI, was achieved via reduction of [((Ph2PPr)PDI)MoI][I] with equimolar Na/naphthalene. This complex was found to have a near octahedral coordination geometry by single crystal X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopy revealed an unpaired Mo-based electron which is highly delocalized onto the PDI chelate core. Attempts to prepare a Mo(i) monohydride complex upon adding NaEt3BH to ((Ph2PPr)PDI)MoI resulted in disproportionation to yield an equimolar quantity of (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoH and newly identified ((Ph2PPr)PDI)MoH2. Independent preparation of ((Ph2PPr)PDI)MoH2 was achieved by adding 2 equiv. NaEt3BH to [((Ph2PPr)PDI)MoI][I] and a minimum hydride resonance T1 of 176 ms suggests that the Mo-bound H atoms are best described as classical hydrides. Interestingly, ((Ph2PPr)PDI)MoH2 can be converted to (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoI upon iodomethane addition, while ((Ph2PPr)PDI)MoH2 is prepared from (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoI in the presence of excess NaEt3BH. Similarly, (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoI can be converted to (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoH with 1 equiv. of NaEt3BH, while the opposite transformation occurs following iodomethane addition to (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoH. Facile interconversion between [((Ph2PPr)PDI)MoI][I], (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoI, (κ(6)-P,N,N,N,C,P-(Ph2PPr)PDI)MoH, and ((Ph2PPr)PDI)MoH2 is expected to guide future reactivity studies on this unique set of compounds.

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Cyclic and Non-Cyclic Pi Complexes of Molybdenum

Wang

Zhai

Hou

2022

Comprehensive Organometallic Chemistry IV

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Electronic structure and spectroscopy of the cycloheptatrienyl molybdenum halide complexes [MoBrL2(η-C7H7)]+ (L2= 2CO, n= 0; L2= 2,2′-bipyridyl, n= 0 or 1)

Cited by 3 publications

References 46 publications

New Phosphorus Compounds K[pcl3(x)] (X= Scn, Cn): Preparation and DFT and Spectroscopic Studies

New Phosphorus Compounds K[pcl3(x)] (X= Scn, Cn): Preparation and DFT and Spectroscopic Studies

Isolation of a bis(imino)pyridine molybdenum(i) iodide complex through controlled reduction and interconversion of its reaction products

Cyclic and Non-Cyclic Pi Complexes of Molybdenum

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