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| {{chembox | {{chembox | ||
| | Verifiedfields = changed | |||
| ⚫ | | verifiedrevid = |
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| | Watchedfields = changed | |||
| | ImageFileL1 =Nikkeloceen.png | |||
| ⚫ | | verifiedrevid = 386829025 | ||
| | ImageSizeL1 = 100px | |||
| | |
| ImageFileL1 = Nickelocene.svg | ||
| | |
| ImageNameL1 = Nickelocene | ||
| | ImageFileR1 = Nickelocene-3D-vdW.png | |||
| | ImageSizeR1 = 140px |
| ImageSizeR1 = 140px | ||
| | ImageNameR1 = Space-filling model of nickelocene | |||
| | ImageCaption2 = Nickelocene freshly depositied on a ] | |||
| | ImageFile2 = Cp2NiSublimate.jpg | |||
| | |
| ImageNameR1 = Space-filling model of nickelocene | ||
| | ImageFile2 = Nickelocen an einem Kühlfinger.jpg | |||
| ⚫ | | |
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| | PIN = Nickelocene<ref>{{cite book |author=] |date=2014 |title=Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013 |publisher=] |pages=1041 |doi=10.1039/9781849733069 |isbn=978-0-85404-182-4}}</ref> | |||
| ⚫ | | Section1 = {{Chembox Identifiers | ||
| ⚫ | | OtherNames = Bis(cyclopentadienyl) nickel(II) | ||
| ⚫ | | |
||
| ⚫ | | Section1 = {{Chembox Identifiers | ||
| ⚫ | | CASNo_Ref = {{cascite|correct|CAS}} | ||
| | CASNo = 1271-28-9 | | CASNo = 1271-28-9 | ||
| | UNII_Ref = {{fdacite|correct|FDA}} | |||
| ⚫ | | |
||
| | |
| UNII = JR8F745XV5 | ||
| | ChEBI_Ref = {{ebicite|correct|EBI}} | |||
| ⚫ | | ChEBI = 30679 | ||
| | RTECS = QR6500000 | |||
| | PubChem = 13628993 | |||
| | ChemSpiderID = 56178 | |||
| | Gmelin = 3412 | |||
| | EC_number = 215-039-0 | |||
| | UNNumber = 1325 3082 | |||
| | StdInChI=1S/2C5H5.Ni/c2*1-2-4-5-3-1;/h2*1-5H;/q2*-1;+2 | |||
| | StdInChIKey = KZPXREABEBSAQM-UHFFFAOYSA-N | |||
| | SMILES = C1=C(C=C1)..(C=C2)C=C2 | |||
| }} | }} | ||
| | Section2 = {{Chembox Properties | | Section2 = {{Chembox Properties | ||
| | |
| Formula = C<sub>10</sub>H<sub>10</sub>Ni | ||
| | |
| MolarMass = 188.88 g/mol | ||
| | |
| Appearance = Green crystals | ||
| | |
| Density = 1.47 g/cm<sup>3</sup> | ||
| | |
| Solubility = insoluble | ||
| | |
| MeltingPtC = 171 to 173 | ||
| | MeltingPt_notes = | |||
| }}<!-- | }}<!-- | ||
| | ] conditions | | ] conditions | ||
| | 60 °C at 0.1 |
| 60 °C at 0.1 mmHg | ||
| |- | |- | ||
| --> | --> | ||
| | Section3 = {{Chembox Structure | | Section3 = {{Chembox Structure | ||
| | |
| Coordination = D<sub>5h</sub>, D<sub>5d</sub> | ||
| | |
| CrystalStruct = | ||
| | |
| Dipole = 0 ] | ||
| }} | }} | ||
| | Section7 = {{Chembox Hazards | | Section7 = {{Chembox Hazards | ||
| | |
| ExternalSDS = | ||
| | GHSPictograms = {{GHS02}}{{GHS07}}{{GHS08}} | |||
| ⚫ | | |
||
| | GHSSignalWord = Danger | |||
| | RPhrases = 49-11-22-43 | |||
| | HPhrases = {{H-phrases|228|302|317|350}} | |||
| | SPhrases = 53-36/37/39-45 | |||
| | PPhrases = {{P-phrases|201|202|210|240|241|261|264|270|272|280|281|301+312|302+352|308+313|321|330|333+313|363|370+378|405|501}} | |||
| ⚫ | | MainHazards = | ||
| | NFPA-H = 2 | |||
| | NFPA-F = 4 | |||
| | NFPA-R = 2 | |||
| | LD50 = 490 mg kg<sup>−1</sup> (oral, rat) <br> 600 mg kg<sup>−1</sup> (oral, mouse) | |||
| }} | }} | ||
| | Section8 = {{Chembox Related | | Section8 = {{Chembox Related | ||
| | |
| OtherCompounds = ], ] | ||
| }} | }} | ||
| }} | }} | ||
| '''Nickelocene''' is the ] with the ] Ni(]-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>. Also known as bis(cyclopentadienyl)nickel or NiCp<sub>2</sub>, this bright green ] solid is of enduring academic interest,<ref>Elschenbroich |
'''Nickelocene''' is the ] with the ] ](]-C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>. Also known as bis(cyclopentadienyl)nickel or NiCp<sub>2</sub>, this bright green ] solid is of enduring academic interest,<ref>{{cite book|last=Elschenbroich |first=C. |title=Organometallics |date=2006 |publisher=Wiley-VCH |location=Weinheim |isbn=978-3-527-29390-2}}</ref> although it does not yet have any known practical applications. | ||
| ==Structure |
==Structure== | ||
| Ni(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> belongs to a group of organometallic compounds called ]s. Metallocenes usually adopt |
Ni(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> belongs to a group of organometallic compounds called ]s. Metallocenes usually adopt structures in which a metal ] is sandwiched between two parallel ] (Cp) rings. In the solid-state, the molecule has D<sub>5d</sub> ], wherein the two rings are ].<ref>{{cite journal|author1=P. Seiler|author2= J. D. Dunitz|title=The structure of nickelocene at room temperature and at 101 K| journal = Acta Crystallogr|year=1980|volume=B36|issue= 10|pages =2255–2260|doi =10.1107/S0567740880008539|s2cid= 93575701}}</ref> | ||
| The Ni center has a formal |
The Ni center has a formal +2 charge, and the Cp rings are usually assigned as ]s (Cp<sup>−</sup>), related to cyclopentadiene by deprotonation. The structure is similar to ]. In terms of its electronic structure, three pairs of d electrons on nickel are allocated to the three d orbitals involved in Ni–Cp bonding: d<sub>''xy''</sub>, d<sub>''x''<sup>2</sup>–''y''<sup>2</sup></sub>, d<sub>''z''<sup>2</sup></sub>. The two remaining d-electrons each reside in the d<sub>''yz''</sub> and d<sub>''xz''</sub> orbitals, giving rise to the molecule's paramagnetism, as manifested in the unusually high field chemical shift observed in its <sup>1</sup>H ]. With 20 ]s, nickelocene has the highest electron count of the transition metal metallocenes. ], Co(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub>, with only 19 valence electrons is, however, a stronger reducing agent, illustrating the fact that electron energy, not electron count determines redox potential. | ||
| ==Preparation== | ==Preparation== | ||
| Nickelocene was first prepared by ] in 1953, shortly after the discovery of ], the first metallocene compound.<ref>{{cite journal | |
Nickelocene was first prepared by ] in 1953, shortly after the discovery of ], the first metallocene compound to be discovered.<ref>{{cite journal | first1=E. O. |last1=Fischer |first2=W. |last2=Pfab | title=Zur Kristallstruktur der Di-Cyclopentadienyl-Verbindungen des zweiwertigen Eisens, Kobalts und Nickels|trans-title=On the crystal structure of biscyclopentadienyl compounds of divalent iron, cobalt and nickel| journal=Z. Naturforsch. B | year=1952 | volume=7 | pages=377–379 |doi=10.1515/znb-1952-0701 |s2cid=93978102 |doi-access=free }}</ref> It has been prepared in a one-pot reaction, by deprotonating cyclopentadiene with ethylmagnesium bromide, and adding anhydrous ].<ref>{{cite journal | last1= Wilkinson |first1=G. |last2=Pauson |first2=P. L.|last3= Cotton|first3= F. A. | title = Bis-cyclopentadienyl Compounds of Nickel and Cobalt | journal = ] | year = 1954 | volume = 76 | doi = 10.1021/ja01636a080 | pages = 1970–4 | issue = 7}}</ref> A modern synthesis entails treatment of anhydrous sources of NiCl<sub>2</sub> (such as ]) with ]:<ref>{{cite book|last1=Girolami |first1=G. S.|last2= Rauchfuss|first2= T. B. |last3=Angelici|first3= R. J.|title= Synthesis and Technique in Inorganic Chemistry|publisher= University Science Books|location= Mill Valley, CA|date= 1999|isbn=0935702482}}</ref> | ||
| :Cl<sub>2</sub> + 2 NaC<sub>5</sub>H<sub>5</sub> → Ni(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> + 2 NaCl + 6 NH<sub>3</sub> | |||
| ==Properties== | |||
| ==Chemical properties== | |||
| Like many organometallic compounds, Ni(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> |
Like many organometallic compounds, Ni(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> does not tolerate extended exposure to air before noticeable decomposition.<ref>{{cite journal | first1=Anna |last1=Jaworska-Augustyniak|first2= Jan |last2=Wojtczak | title=Charge-transfer complexes of cobaltocene and nickelocene with tetrachloromethane | journal=Monatshefte für Chemie | year=1979 | volume=110 | pages=1113–1121 | doi=10.1007/BF00910959 | issue=5|s2cid=91737661 }}</ref> Samples are typically handled with ]s. | ||
| Most chemical reactions of nickelocene are characterized by its tendency to yield ] products with loss or modification of one Cp ring. | Most chemical reactions of nickelocene are characterized by its tendency to yield ] products with loss or modification of one Cp ring. | ||
| :Ni(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> |
:Ni(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> + 4 ] → Ni(PF<sub>3</sub>)<sub>4</sub> + organic products | ||
| The reaction with secondary phosphines follows a similar pattern: | The reaction with secondary phosphines follows a similar pattern: | ||
| :2 Ni(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> + 2 ] → + 2 C<sub>5</sub>H<sub>6</sub> | |||
| Nickelocene can be oxidized to the corresponding cation, which contains Ni(III). | Nickelocene can be oxidized to the corresponding cation, which contains Ni(III). | ||
| Gaseous Ni(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> decomposes to a |
Gaseous Ni(C<sub>5</sub>H<sub>5</sub>)<sub>2</sub> decomposes to a nickel mirror upon contact with a hot surface, releasing the hydrocarbon ligands as gaseous coproducts. This process has been considered as a means of preparing nickel films. | ||
| Nickelocene reacts with ] to produce ], a highly toxic organonickel compound. | |||
| ==References== | ==References== | ||
| Line 72: | Line 94: | ||
| ==External links== | ==External links== | ||
| * | * | ||
| * |
* | ||
| {{Nickel compounds}} | |||
| {{Cyclopentadienide complexes}} | |||
| ] | ] | ||
| ] | ] | ||
| ] | |||
| ] | |||
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Latest revision as of 03:53, 12 December 2024
| |||
 Nickelocene freshly depositied on a cold finger | |||
| Names | |||
|---|---|---|---|
| Preferred IUPAC name Nickelocene | |||
| Other names Bis(cyclopentadienyl) nickel(II) | |||
| Identifiers | |||
| CAS Number | |||
| 3D model (JSmol) | |||
| ChEBI | |||
| ChemSpider | |||
| ECHA InfoCard | 100.013.672 
| ||
| EC Number |
| ||
| Gmelin Reference | 3412 | ||
| PubChem CID | |||
| RTECS number |
| ||
| UNII | |||
| UN number | 1325 3082 | ||
| CompTox Dashboard (EPA) | |||
InChI
| |||
SMILES
| |||
| Properties | |||
| Chemical formula | C10H10Ni | ||
| Molar mass | 188.88 g/mol | ||
| Appearance | Green crystals | ||
| Density | 1.47 g/cm | ||
| Melting point | 171 to 173 °C (340 to 343 °F; 444 to 446 K) | ||
| Solubility in water | insoluble | ||
| Structure | |||
| Coordination geometry | D5h, D5d | ||
| Dipole moment | 0 D | ||
| Hazards | |||
| GHS labelling: | |||
| Pictograms |   
| ||
| Signal word | Danger | ||
| Hazard statements | H228, H302, H317, H350 | ||
| Precautionary statements | P201, P202, P210, P240, P241, P261, P264, P270, P272, P280, P281, P301+P312, P302+P352, P308+P313, P321, P330, P333+P313, P363, P370+P378, P405, P501 | ||
| NFPA 704 (fire diamond) |
 | ||
| Lethal dose or concentration (LD, LC): | |||
| LD50 (median dose) | 490 mg kg (oral, rat) 600 mg kg (oral, mouse) | ||
| Related compounds | |||
| Related compounds | CoCp2, FeCp2 | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa).
 N verify (what is ?)
Infobox references
| |||
Nickelocene is the organonickel compound with the formula Ni(η-C5H5)2. Also known as bis(cyclopentadienyl)nickel or NiCp2, this bright green paramagnetic solid is of enduring academic interest, although it does not yet have any known practical applications.
Structure
Ni(C5H5)2 belongs to a group of organometallic compounds called metallocenes. Metallocenes usually adopt structures in which a metal ion is sandwiched between two parallel cyclopentadienyl (Cp) rings. In the solid-state, the molecule has D5d symmetry, wherein the two rings are staggered.
The Ni center has a formal +2 charge, and the Cp rings are usually assigned as cyclopentadienyl anions (Cp), related to cyclopentadiene by deprotonation. The structure is similar to ferrocene. In terms of its electronic structure, three pairs of d electrons on nickel are allocated to the three d orbitals involved in Ni–Cp bonding: dxy, dx–y, dz. The two remaining d-electrons each reside in the dyz and dxz orbitals, giving rise to the molecule's paramagnetism, as manifested in the unusually high field chemical shift observed in its H NMR spectrum. With 20 valence electrons, nickelocene has the highest electron count of the transition metal metallocenes. Cobaltocene, Co(C5H5)2, with only 19 valence electrons is, however, a stronger reducing agent, illustrating the fact that electron energy, not electron count determines redox potential.
Preparation
Nickelocene was first prepared by E. O. Fischer in 1953, shortly after the discovery of ferrocene, the first metallocene compound to be discovered. It has been prepared in a one-pot reaction, by deprotonating cyclopentadiene with ethylmagnesium bromide, and adding anhydrous nickel(II) acetylacetonate. A modern synthesis entails treatment of anhydrous sources of NiCl2 (such as hexaamminenickel chloride) with sodium cyclopentadienyl:
- Cl2 + 2 NaC5H5 → Ni(C5H5)2 + 2 NaCl + 6 NH3
Properties
Like many organometallic compounds, Ni(C5H5)2 does not tolerate extended exposure to air before noticeable decomposition. Samples are typically handled with air-free techniques.
Most chemical reactions of nickelocene are characterized by its tendency to yield 18-electron products with loss or modification of one Cp ring.
- Ni(C5H5)2 + 4 PF3 → Ni(PF3)4 + organic products
The reaction with secondary phosphines follows a similar pattern:
- 2 Ni(C5H5)2 + 2 PPh2H → + 2 C5H6
Nickelocene can be oxidized to the corresponding cation, which contains Ni(III).
Gaseous Ni(C5H5)2 decomposes to a nickel mirror upon contact with a hot surface, releasing the hydrocarbon ligands as gaseous coproducts. This process has been considered as a means of preparing nickel films.
Nickelocene reacts with nitric acid to produce cyclopentadienyl nickel nitrosyl, a highly toxic organonickel compound.
References
- International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 1041. doi:10.1039/9781849733069. ISBN 978-0-85404-182-4.
- Elschenbroich, C. (2006). Organometallics. Weinheim: Wiley-VCH. ISBN 978-3-527-29390-2.
- P. Seiler; J. D. Dunitz (1980). "The structure of nickelocene at room temperature and at 101 K". Acta Crystallogr. B36 (10): 2255–2260. doi:10.1107/S0567740880008539. S2CID 93575701.
- Fischer, E. O.; Pfab, W. (1952). "Zur Kristallstruktur der Di-Cyclopentadienyl-Verbindungen des zweiwertigen Eisens, Kobalts und Nickels" [On the crystal structure of biscyclopentadienyl compounds of divalent iron, cobalt and nickel]. Z. Naturforsch. B. 7: 377–379. doi:10.1515/znb-1952-0701. S2CID 93978102.
- Wilkinson, G.; Pauson, P. L.; Cotton, F. A. (1954). "Bis-cyclopentadienyl Compounds of Nickel and Cobalt". J. Am. Chem. Soc. 76 (7): 1970–4. doi:10.1021/ja01636a080.
- Girolami, G. S.; Rauchfuss, T. B.; Angelici, R. J. (1999). Synthesis and Technique in Inorganic Chemistry. Mill Valley, CA: University Science Books. ISBN 0935702482.
- Jaworska-Augustyniak, Anna; Wojtczak, Jan (1979). "Charge-transfer complexes of cobaltocene and nickelocene with tetrachloromethane". Monatshefte für Chemie. 110 (5): 1113–1121. doi:10.1007/BF00910959. S2CID 91737661.
External links
- IARC Monograph "Nickel and Nickel compounds"
- National Pollutant Inventory – Nickel and compounds Fact Sheet
| Nickel compounds | |
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| Nickel(0) | |
| Nickel(II) | |
| Nickel(III) | |
| Nickel(IV) | |
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