Dataset Information

Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV).

ABSTRACT: The reaction of [Zr(Tren^DMBS )(Cl)] [Zr1; Tren^DMBS =N(CH₂ CH₂ NSiMe₂ Bu^t )₃ ] with NaPH₂ gave the terminal parent phosphanide complex [Zr(Tren^DMBS )(PH₂ )] [Zr2; Zr-P=2.690(2)?Å]. Treatment of Zr2 with one equivalent of KCH₂ C₆ H₅ and two equivalents of benzo-15-crown-5 ether (B15C5) afforded an unprecedented example (outside of matrix isolation) of a structurally authenticated transition-metal terminal parent phosphinidene complex [Zr(Tren^DMBS )(PH)][K(B15C5)₂ ] [Zr3; Zr=P=2.472(2)?Å]. DFT calculations reveal a polarized-covalent Zr=P double bond, with a Mayer bond order of 1.48, and together with IR spectroscopic data also suggest an agostic-type Zr???HP interaction [?_ZrPH =66.7°] which is unexpectedly similar to that found in cryogenic, spectroscopically observed phosphinidene species. Surprisingly, computational data suggest that the Zr=P linkage is similarly polarized, and thus as covalent, as essentially isostructural U=P and Th=P analogues.

SUBMITTER: Stafford H

PROVIDER: S-EPMC5575506 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature

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Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV).

Stafford Hannah H Rookes Thomas M TM Wildman Elizabeth P EP Balázs Gábor G Wooles Ashley J AJ Scheer Manfred M Liddle Stephen T ST

Angewandte Chemie (International ed. in English) 20170526 26

The reaction of [Zr(TrenDMBS )(Cl)] [Zr1; TrenDMBS =N(CH2 CH2 NSiMe2 But )3 ] with NaPH2 gave the terminal parent phosphanide complex [Zr(TrenDMBS )(PH2 )] [Zr2; Zr-P=2.690(2) Å]. Treatment of Zr2 with one equivalent of KCH2 C6 H5 and two equivalents of benzo-15-crown-5 ether (B15C5) afforded an unprecedented example (outside of matrix isolation) of a str ...[more]

PMID: 28489308

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Project description:Metalloporphyrin and metallophthalocyanine dyes ligating Hf(IV) and Zr(IV) ions bind to semiconductor oxide surfaces such as TiO(2) via the protruding group IV metal ions. The use of oxophylic metal ions with large ionic radii that protrude from the macrocycle is a unique mode of attaching chromophores to oxide surfaces in the design of dye-sensitized solar cells (DSSCs). Our previous report on the structure and physical properties of ternary complexes wherein the Hf(IV) and Zr(IV) ions are ligated to both a porphyrinoid and to a defect site on a polyoxometalate (POM) represents a model for this new way of binding dyes to oxide surfaces. The Zr(IV) and Hf(IV) complexes of 5,10,15,20-tetraphenylporphyrin (TPP) with two ligated acetates, (TPP)Hf(OAc)(2) and (TPP)Zr(OAc)(2), and the corresponding metallophthalocyanine (Pc) diacetate complexes, (Pc)Hf(OAc)(2) and (Pc)Zr(OAc)(2), were evaluated as novel dyes for the fabrication of dye-sensitized solar cells. Similarly to the ternary complexes with the POM, the oxide surface replaces the acetates to affect binding. In DSSCs the Zr(IV) phthalocyanine dye performs better than the Zr(IV) porphyrin dye, and reaches an overall efficiency of ~ 1.0%. The Hf(IV) dyes are less efficient. The photophysical properties of these complexes in solution suggested energetically favorable injection of electrons into the conduction band of TiO(2) semiconductor nanoparticles, as well as a good band gap match with I(3) (-)/I(-) pair in liquid 1-butyl-3-methyl imidazolium iodide. The combination of blue absorbing TPP with the red absorbing Pc complexes can increase the absorbance of solar light in the device; however, the overall conversion efficiency of DSSCs using TiO(2) nanoparticles treated with a mixture of both Zr(IV) complexes is comparable, but not greater than, the single (Pc)Zr. Thus, surface bound (TPP)Zr increases the absorbance in blue region of the spectra, but at the cost of diminished absorbance in the red in this DSSC architecture.

Dataset Information

Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV).

Publications

Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV).

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