Questions tagged [transition-metals]

For questions about the characteristic physical properties, chemical reactions, etc. of d-block elements, group 3-12, or their compounds. Do not use this tag if your questions is about general properties of metals, use [metal] instead. Also see [rare-earth-elements].

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f-electrons in chemistry of heavy transition metals

In one lecture on recent MCR-X conference I was puzzled by a side-note "f-hole is critical to describe DoS of $\ce{IrO2}$ correctly." The context was DFT periodic plane-wave calculations with ...
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228 views

What is d-orbital collapse?

When I was perusing the works of Schwarz on atomic structure, I came across the unfamiliar term of d-orbital collapse. He describes it as a variation in energetic sequence from group 1 to 3 elements ...
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Mechanism for an Étard reaction (chromium complex)

In the following reaction, a chromium complex is formed during the Étard reaction: I have the following questions: How is this complex formed? How does its hydrolysis take place? (What's the ...
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260 views

Why does tantalum and tungsten not form amalgam?

User @Poutnik has recently answered a question in which he/she quoted this statement from Wikipedia: Almost all metals can form amalgams with mercury, the notable exceptions being iron, platinum, ...
7
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1answer
2k views

Why does iron have an abnormally high ionization energy?

Along a period the ionization energy should increase because the atomic number is increasing, but there is negligible increase in shielding. However, $\mathrm{IE}_\ce{Mn} < \mathrm{IE}_\ce{Fe} > ...
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52 views

Are platinum metal whiskers very unusual?

Over 20 years ago I pulled my first set of platinum spark plugs out of a car because the engine was missing badly. Two of the six plugs each had one whisker in the gap between electrodes. One crossed ...
6
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717 views

“Alternative” derivation of the spin-only formula

The spin-only formula $$\mu_\mathrm{so} = \mu_\mathrm{B} \sqrt{n(n+2)} = \mu_\mathrm{B}\cdot 2\sqrt{S(S+1)}$$ is usually a good first approximation to calculate the magnetic moment of transition ...
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33 views

Removal of nickel plating on MgB2 without damaging the boride?

I need to remove a nickel plating of a MgB2 wire without causing damage to the MgB2. I felt that electrolysis is the best method but I do not know what electrolyte to use for this. I also need to coat ...
6
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3k views

Is iron(III) carbonate stable in water?

I searched for this onsite already, and also found the following answer on Quora: In aqueous environment, iron(III) is bound by water molecules and exists as $\ce{[Fe(H2O)6]^3+}$. Due to strong ...
6
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178 views

I found transition states (TS), but calculations aren't supported by experiment. Do I look for more TSs or somewhere else?

I'm using Gaussian to investigate a catalyst system. Experimental evidence showed that one of three analogues (R = phenyl, Ph), yielded a benzosultam when treated with 2,4,6-...
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713 views

Why are the electronegativities of transition metals so similar to each other?

I was wondering why the electronegativity among transition metals are so similar. I can't find anything on the internet, just vague answers about the d orbitals that don't seem to provide a sufficient ...
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30 views

Molecular orbital diagram for carbene-metal and carbodiphosphorane-metal interaction

I am interested in understanding how carbenes and carbodiphosphoranes interact differently with a transition metals. I would like to use qualitative molecular orbital theory arguments (with an ...
5
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39 views

Cytotoxicity of Ru-complexes

I have a basic question: why are Ru(II)-complexes cytotoxic? What I know is that depending on the used ligand some of them interact with the DNA either via DNA-pi-stacking (intercalation) or binding ...
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128 views

Toxicity of vanadium in pottery

I mix and develop glaze recipes for midfire stoneware (fired to 1220°C). The colorants in pottery are mostly iron, copper, cobalt, tin, titanium, chrome, and a few other transition metals. Many of ...
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108 views

Relative orbital energies of Mn and Ni

In this MO diagram, why are the atomic Mn $3d$ orbitals higher in energy than the Ni $3d$ orbitals?
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363 views

Calculation of Bond/Angle/Dihedral force constant

I am a big fan of Mopac (Though I have a very little knowledge about the tool). I have some queries regarding some calculations in Mopac2016: Problem: How to calculate Bond or Angle or Dihedral ...
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3k views

Why does reduction of naphthalene with nickel/hydrogen lead to trans-decalin?

Is there any reason why $\ce{H2/Ni}$ leads to trans-decalin? I knew from high school that catalytic hydrogenations are always syn.
5
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186 views

How to rationalise the trend in the covalent radii of the transition metals?

Why do the covalent radii of transition series decrease at the start rapidly, then become almost constant and at the end of series begin to increase from left to right in periodic table?
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Rhombohedral second-order Jahn–Teller effect in Au(II) complex?

I was recently listening to a talk about the following work[1] when the author mentioned that they explained the following. In this $\ce{Au(II)}$-porphyrin complex you observe two sets of $\ce{Au-N}$ ...
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Why is the geometry of [Ni(CN)4)]2- square planar? Why is it colorless?

Why is the geometry of $\ce{[Ni(CN)4)]^{2-}}$ square planar given that it has a coordination number of 4? Shouldn't its geometry be tetrahedral as it would minimise the bond angle and hence repulsion?...
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478 views

Why doesn't beta hydride elimination happen in alkenyl/aryl halides?

Beta hydride elimination is an important reaction in organometallic chemistry: This reaction prohibits the use of saturated alkyl halides in coupling reactions, because it can take place after ...
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139 views

Asymmetric Suzuki coupling - saturated alkyl chain

9-BBN is applied for Suzuki coupling of a saturated alkyl chain with some alkenyl,alkynyl or even secondary alkyl halide like the modification attached: (Saito, B.; Fu, G. C. Alkyl−Alkyl Suzuki Cross-...
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603 views

Can oxidation of ethanol by copper(II) oxide yield copper(I) oxide as one of the products?

We know that ethanol is oxidised by copper(II) oxide to an aldehyde. Copper is reduced from $\ce{Cu^2+}$ to $\ce{Cu}$. Can this reaction, with some specific condition, yield $\ce{Cu2O}$ instead? That ...
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1answer
2k views

Titanium in HF vs HCl

So we tried the reaction between Titanium metal with hydrochloric acid and hydrofluoric acid at a similar concentration. While boiling temperatures and constant heat over a long period of time are ...
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199 views

Why are the Covalent Radii of Ruthenium and Osmium So Similar?

Osmium and Ruthenium have covalent radii 144 and 146 respectively (according to Wikipedia). How are these values so similar when Osmium has 32 more electrons, with another filled p, s, and f orbital ...
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105 views

Dilute FeCl3 colour is darker at 5e-4M than at 5e-3M. Why?

I did two different dilutions of $\ce{FeCl3}$ (within a $\pu{1h}$ timespan) from $\pu{0.05 M}$, and the one with $\pu{5E-4 M}$ concentration looked a darker orange than the one with $\pu{5E-3 M}$. ...
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63 views

Why does some compound as given in the image below change from low spin to high spin above a particular transition temperature?

Magnetic moment sudden increase at a particular temperature is explained by CFT. But why does it happen at all?
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353 views

Why is cupric oxide more basic than cuprous oxide?

I have learnt earlier that metal oxides with higher metal oxidation states are more acidic than those with less oxidation states, but copper disobeys this rule. Why?
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145 views

Do amino groups need to be protected during a Clemmensen reduction?

In class, we learned about the Clemmensen reduction of carbonyl groups to the corresponding hydrocarbon. This is all well and good, except that it would also seem that the conditions used in the ...
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41 views

Are there any stable complexes where an (N-unsubstituted) imine is bound eta^2 to a (late) transition metal?

I've been looking for an example of a stable complex where a $\ce{C=N}$ is coordinated $\eta^2$ to a (late) transition metal, but could not find any. Do they exist at all? For $\ce{C=C}$ there are ...
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155 views

What is the structure of diferric hexaphenolate?

I was studying about the ferric chloride identification of phenol, where one product formed is diferric hexaphenolate. But I am having trouble drawing out the structure of it. With ferric ion having a ...
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56 views

How do partially protonated sulfate ligands affect a metal's charge?

I'm currently reviewing the Periana-Catalytica system and I have a question about one of the intermediates, namely $\ce{[(bpym)Pt(OSO3H)2]^+}$, which is found in the following tutorial review. How do ...
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211 views

Why do isomeric bis-ethylenediamine cobalt complexes react differently?

A compound $\ce{Co(en)2(NO2)2Cl}$ has been prepared in a number of isomeric forms.One form undergoes no reaction with $\ce{AgNO3}$ or $\ce{(en)}$ and is optically inactive. A second form reacts with $...
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1k views

How can I dissolve copper but not zinc?

I have a zinc-body garden spray head with a brass garden hose thread stuck inside. This is actually an irritatingly common problem. Which got me wondering: What chemical means exist to dissolve ...
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127 views

Iron (II) dioxygen reaction mechanism?

Ok so I'm confused about the mechanism for this process: Now the idea here is that iron first becomes oxidised to Fe(III) by placing an electron in the antibonding orbital of dioxygen. This is ...
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43 views

Is hydrolytic polymerisation the mechanism by which the precipitate forms from the neutral complex?

From basic coordination chemistry and acid-base equilibria we understand that a metal hexa-aqua ion can be deprotonated until it's positive charge is balanced by the negative charge of the hydroxides ...
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33 views

Ionic radius for tetrahedral metal–ligand complexes

The ionic radii for metal–ligand complexes that are in an octahedral coordination are easy to find. I understand that when the $\mathrm{e_g}$ orbital is filled, the ionic radius increases because the ...
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40 views

Liquid storage of transition metal oxides?

Transition metal oxides (TMOs) have a lot of interesting properties, from ferroelectricity to battery applications. Often times you can change the properties with only slight changes of oxygen ...
2
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1answer
53 views

Determination of spinel structure by CFSE

$\ce{CuFe2O4}$ has inverse spinel structure, but $\ce{ZnFe2O4}$ has normal spinel structure. Explain. I know that normal spinels have a structure like $\ce{(A^{II})^{tet}(B^{III})^{oct}_2O_4}$-like ...
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0answers
132 views

Colour of VO3^-?

To aquire the yellow colour of vanadium ion, it must be present in a 5+ oxdiation state. This can be acheived (according to my textbook) by adding dilute sulfuric acid to $\ce{NH4VO3}$, then followed ...
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1k views

Explain why can't zinc be plated out from a Zn(II) solution using standard reduction potentials

I am currently learning about electrochemistry using Zumdahl's Chemistry [1, pp. 709–710]. One of the critical thinking questions is Why can $\ce{Zn}$ not be plated out from an aqueous solution of $\...
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146 views

Factors that influence the electrical conductivity of metals

The electrical conductivity of metals is a physical property of these materials. Much of the theory used to explain the electrical conductivity of metals is also based on physics understanding. ...
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60 views

Reactivity of Ni Vs. Pd - available oxidation states

I'm hoping someone can help me tighten up my understanding of the origins of the differences between Ni and Pd catalysis. I understand that Ni has higher charge density and this is the reason for it'...
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72 views

Can hexavalent chromium be created by exposure of chromium alloys to air at room temperature?

I believe that Cr on its own (as in chrome coating) oxidizes as Cr(III) when exposed to air, and similarly I think that it is the same for Cr as a component of stainless steel. Is it always the case ...
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2answers
3k views

Density of d-block elements

Something that confuses me slightly is the trends in density when comparing periods 4, 5, and 6 in the d-block. Looking at periods 5 and 6, the density peaks at group 8, with ruthenium and osmium, ...
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306 views

Molecular orbital diagram for terminal metal-oxo complex with dative bonds

I am interested in terminal metal-oxo complexes and their electronic structure, specifically those with coordination numbers of 6, including the oxo ligand. I know that Fe(IV)-oxo complexes tend to ...
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0answers
5k views

The irregular trend in ionization enthalpy of 3d elements

The d block elements display several exceptional behaviours, and one of them is the irregular trend in ionization enthalpy of 3d elements. The reason given by my textbook is very confusing, which I'...
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31 views

Trend in the infrared stretching of molecular hydrogen to group 8 transitions metals?

While going through old notes, in relation to the Dewar-Chatt-Duncanson model, it states that the stretching frequency for $\ce{N2}$ to the group 8 transition metals ($\nu(\ce{NN})$) proceeds as: \...
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297 views

Are lustre and conductivity directly related?

In a question that I had asked before, Is chromium the shiniest metal?, I received the answer that silver was, in fact the most lustrous metal for visible wavelengths. At the same time, silver is also ...
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293 views

metallic bonding in transition metal sulfides

I searched on the internet but failed to find a clear solution for this question: Regarding transition metal sulfides like NiS or FeS, is there metallic bonding within their crystal structure? If ...