Presentations IIb

Presentations IIb - Ti(0 and Ti(IV Ti has oxidation states...

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Ti(0) and Ti(IV) Ti has oxidation states of +4, +3, +2, and 0 Ti wire dissolves in aqueous HF 0 +1 -1 +4 0 2Ti + 6HF → *TiF₆+ 2⁻ + Ti(II) + 3H₂ Ti reacts with most non-metals when heated For example, Ti reacts with O₂ and forms TiO₂ (rutile structure type) Central Ti: Octahedral geometry and point group O:Trigonal Planar, bent Ti(IV) halides are formed from the elements (TiF₄, TiCl₄, TiBr₄, TiI₄) TiF₄ forms HF when it reacts with water (TiCl₄ and TiBr₄ hydrolyze faster) TiCl₄ is used with AlCl₃ in Ziegler -Natta catalyst for alkene polymerization TiO₂ and TiCl₄ react: +4 +4 -1 -1 +4 +4 TiO₂ + TiCl₄ → *Cl₃TiOTiCl₃+ -1 +4 +4 +1 -1 +1 +4 *Cl₃TiOTiCl₃+ + *Et₄N+Cl → *Et₄N+₂*TiOCl₄+ Housecroft 691-694
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Ti(0) and Ti(IV) TiF is T d point group F, Cl are sigma bases so weakly split d-orbitals on Ti TiCl₄ IR and Raman Spectra: 9 modes total 4 stretches and 5 bends
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Rhodium (II) Mononuclear forms of Rh(II) are rare Adopt [Rh 2 (μ-L) 4 ] or [Rh 2 (μ-L) 4 L 2 ] Carboxylate bridges most common [RCOO] - Other bridging ligands include [RCONH] - and [RCOS] - Synthesis 𝑅𝑅𝑅𝑙 3 3 𝐻 2 𝑂 𝑀𝑒𝑒𝑂 2 𝑀𝑒𝑂𝑒 𝑅𝑅 2 𝜇 2 − 𝑂 2 𝑅𝐶𝐶 4 𝐶𝐶𝑂𝐻 2 𝑅𝑅𝑅𝑙 6 𝑀𝑒𝑒𝑂 2 𝑒 𝐸𝐸𝑂𝑒 , 𝑒 2 𝑂 𝑅𝑅 2 𝜇 2 − 𝑂 2 𝑅𝐶𝐶 4 𝑂𝐻 2 2 Axial ligands can be removed by heating in vacuo or replaced Electronics Formally {Rh 2 } 4+ Rh-Rh single bond Pg 683
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HOMO: Pi antibonding with O bridging ligands. No electron density on bridging carbon LUMO: Antibonding C- O bonds 𝑅𝑅 2 𝜇 2 𝑂 2 𝑅𝐶𝐶 4 𝑂𝐻 2 2 6-31G Basis set does not have enough orbitals to simulate Rh, so I used SDD Note: Double bonds in these pictures are inaccurate, but were necessary for Gaussian to display the correct geometry.
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