Showed that a nickel complex could be formed from a mono-0-ether derivative of benzildioxime. A further modification of the structural formula for nickel dimethylglyoxime was proposed by Brady and Muers (10), fhey reacted the compound with methyl magnesium iodide and found that no methane was formed. As a result, they sug.
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| ECHA InfoCard | 100.002.201 |
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| Properties | |
| C4H8N2O2 | |
| Molar mass | 116.120 g·mol−1 |
| Appearance | White/Off White Powder |
| Density | 1.37 g/cm3 |
| Melting point | 240 to 241 °C (464 to 466 °F; 513 to 514 K) |
| Boiling point | decomposes |
| low | |
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| 0 | |
| Hazards | |
| Main hazards | Toxic, Skin/Eye Irritant |
| Safety data sheet | External MSDS |
| GHS pictograms | |
| GHS Signal word | Danger |
| H228, H301 | |
| P210, P240, P241, P264, P270, P280, P301+310, P321, P330, P370+378, P405, P501 | |
| NFPA 704 (fire diamond) | |
| Related compounds | |
| Hydroxylamine salicylaldoxime | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
| verify (what is ?) | |
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Dimethylglyoxime is a chemical compound described by the formula CH3C(NOH)C(NOH)CH3. Its abbreviation is dmgH2 for neutral form, and dmgH for anionic form, where H stands for hydrogen. This colourless solid is the dioxime derivative of the diketone butane-2,3-dione (also known as diacetyl). DmgH2 is used in the analysis of palladium or nickel. Its coordination complexes are of theoretical interest as models for enzymes and as catalysts. Many related ligands can be prepared from other diketones, e.g. benzil.
Preparation[edit]
Dimethylglyoxime can be prepared from butanone first by reaction with ethyl nitrite to give biacetyl monoxime. The second oxime is installed using sodium hydroxylamine monosulfonate:[1]
Complexes[edit]
Dimethylglyoxime is used to detect and quantify nickel, which forms the bright red complex nickel bis(dimethylglyoximate) (Ni(dmgH)2). The reaction was discovered by L. A. Chugaev in 1905.[2]
Cobalt complexes have also received much attention. In chloro(pyridine)cobaloxime[3] the macrocycle [dmgH]22− mimics the macrocyclic ligand found in vitamin B12.
References[edit]
- ^Semon, W. L.; Damerell, V. R. (1930). 'Dimethylglyoxime'. Organic Syntheses. 10: 22. doi:10.15227/orgsyn.010.0022.CS1 maint: multiple names: authors list (link)
- ^Lev Tschugaeff (1905). 'Über ein neues, empfindliches Reagens auf Nickel'. Berichte der Deutschen Chemischen Gesellschaft. 38 (3): 2520–2522. doi:10.1002/cber.19050380317.
- ^Girolami, G.. S.; Rauchfuss, T.B.; Angelici, R. J. (1999). Synthesis and Technique in Inorganic Chemistry: A Laboratory Manual (3rd ed.). pp. 213–215.
1) Amongst Ni(CO)4, [Ni(CN)4]2- and NiCl42-:
(IIT JEE 1991)
a) Ni(CO)4 and NiCl42- are diamagnetic; and [Ni(CN)4] 2- is paramagnetic.
b) [Ni(CN)4]2- and NiCl42- are diamagnetic; and Ni(CO)4 is paramagnetic.
c) Ni(CO)4 and [Ni(CN)4]2- are diamagnetic; and NiCl42- is paramagnetic.
d) Ni(CO)4 is diamagnetic; [Ni(CN)4]2- and NiCl42- are paramagnetic.
Logic & Solution:
Ni(CO)4 = Ni + 4CO
* The valence shell electronic configuration of ground state Ni atom is 3d8 4s2.
* All of these 10 electrons are pushed into 3d orbitals and get paired up when strong field CO ligands approach Ni atom. The empty 4s and three 4p orbitals undergo sp3 hybridization and form bonds with CO ligands to give Ni(CO)4. Thus Ni(CO)4 is diamagnetic.
KEY POINTS:
Structure Of Ni Dmg Complex System
Ni(CO)4 Hybridization:sp3
Ni(CO)4 Shape & Structure (geometry): Tetrahedral
Ni(CO)4 Magnetic nature: Diamagnetic (low spin)
[Ni(CN)4]2- = Ni2+ + 4CN-
* In [Ni(CN)4]2-, there is Ni2+ ion for which the electronic configuration in the valence shell is 3d8 4s0.
* In presence of strong field CN- ions, all the electrons are paired up. The empty 4d, 3s and two 4p orbitals undergo dsp2 hybridization to make bonds with CN- ligands in square planar geometry. Thus [Ni(CN)4]2- is diamagnetic.
KEY POINTS:
[Ni(CN)4]2- Hybridization:dsp2
[Ni(CN)4]2- Shape: Square planar
[Ni(CN)4]2- Magnetic nature: Diamagnetic (low spin)
NiCl42-= Ni2+ + 4Cl-
* Again in NiCl42-, there is Ni2+ ion, However, in presence of weak field Cl- ligands, NO pairing of d-electrons occurs. Therefore, Ni2+ undergoes sp3 hybridization to make bonds with Cl- ligands in tetrahedral geometry. As there are unpaired electrons in the d-orbitals, NiCl42- is paramagnetic and is referred to as a high spin complex.
KEY POINTS:
[NiCl4]2- Hybridization:sp3
[NiCl4]2- Shape & Structure: Tetrahedral
[NiCl4]2- Magnetic nature: Paramagnetic (low spin)
Conclusion:
The correct option is 'c'.
Related questions
2) Among the following the lowest degree of paramagnetism per mole of the compound at 298 K will be shown by:
(IIT JEE 1988)
a) MnSO4.4H2O
b) CuSO4.5H2O
c) FeSO4.6H2O
d) NiSO4.6H2O
Logic & solution:
* In presence of water, which is a weak field ligand, the configurations of metal ions in hydrated compounds reflect those in isolated gaseous ions i.e., no pairing of electrons is possible as the interaction with water molecules is weak.
* All the metal ions in the above compounds are divalent and their outer shell electronic configurations are shown below.
* The paramagnetic nature of a compound is proportional to the number of unpaired electrons in it. Mn2+ ion has more number of unpaired electrons. Hence MnSO4.4H2O shows greater paramagnetic nature.
Structure Of Ni Dmg Complex 5
Whereas there is only one unpaired electron in Cu2+ and hence CuSO4.5H2O shows lowest degree of paramagnetism.
Conclusion:
Correct option is: 'b'.
3) Among the following ions which one has the highest paramagnetism?
(IIT JEE 1993)
a) [Cr(H2O)6]3+
b) [Fe(H2O)6]2+
c) [Cu(H2O)6]2+
d) [Zn(H2O)6]2+
Logic & solution:
* As mentioned in previous question, the electronic configuration of metal ions is not much affected by weak field ligand water. Hence the electronic configurations of metal ions coordinated to water are same as in isolated ions.
* The outer shell electronic configurations of metal ions in the above complexes are shown below.
* Fe2+ ion has more number of unpaired electrons. Hence [Fe(H2O)6]2+ is more paramagnetic.
Note: The charge on metal ions is equal to the charge on the complex since water is a neutral ligand.
Conclusion:
Correct option is: 'b'.
4) Transition metals show paramagnetic behavior. This is because of their :
Structure Of Ni Dmg Complex Free
(AFMC 2009)
A) high lattice energy
B) variable oxidation state
C) characteristic configuration
D) unpaired electrons
Conclusion:
Correct option is: D
Structure Of Ni(dmg)2 Complex
Homework
1) How do you calculate the magnetic moment of ions of transition elements?
2) What are the strong field and weak field ligands?
3) Why Ti(SO4)2 is diamagnetic?
4) What is the hybridization & structure of [CoCl4]2-? What is the magnetic nature of this compound?
Structure Of Ni Dmg Complex 2
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