Transition metal alkyne complex: Difference between revisions
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==Synthesis== |
==Synthesis== |
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Transition metal alkyne complexes are often formed by the displacement of labile ligands by the alkyne. For example, a variety of cobalt-alkyne complexes |
Transition metal alkyne complexes are often formed by the displacement of labile ligands by the alkyne. For example, a variety of [[dicobalt hexacarbonyl acetylene complex|cobalt-alkyne complexes]] arise by the reaction of alkynes with dicobalt octacarbonyl.<ref>Kemmitt, R. D. W.; Russell, D. R.; "Cobalt" in ''Comprehensive Organometallic Chemistry I''; Abel, E.W.; Stone, F.G.A.; Wilkinson, G. eds., 1982, Pergamon Press, Oxford. {{ISBN|0-08-025269-9}}</ref> |
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:{{chem2|Co2(CO)8 + R2C2 -> (R2C2)Co2(CO)6 + 2 CO}} |
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Many alkyne complexes are produced by reduction of metal halides:<ref>{{cite journal|doi=10.1021/om0208570|title=The Titanocene Complex of Bis(trimethylsilyl)acetylene: Synthesis, Structure, and Chemistry|year=2003|last1=Rosenthal|first1=Uwe|last2=Burlakov|first2=Vladimir V.|last3=Arndt|first3=Perdita|last4=Baumann|first4=Wolfgang|last5=Spannenberg|first5=Anke|journal=Organometallics|volume=22|issue=5|pages=884–900}}</ref> |
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: Cp<sub>2</sub>TiCl<sub>2</sub> + Mg + Me<sub>3</sub>SiC≡CSiMe<sub>3</sub> → Cp<sub>2</sub>Ti[(CSiMe<sub>3</sub>)<sub>2</sub>] + MgCl<sub>2</sub> |
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Many alkyne complexes are produced by reduction of metal halides, e.g. [[titanocene dichloride]] and [[bis(triphenylphosphine)platinum dichloride]] in the presence of the alkyne: |
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: Cp<sub>2</sub>TiCl<sub>2</sub> + C<sub>2</sub>R<sub>2</sub> + Mg → Cp<sub>2</sub>Ti(C<sub>2</sub>R<sub>2</sub>) + MgCl<sub>2</sub> |
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[[File:VarietyPackAlkyneCmpx.svg|thumb|center|620px|Structures of various metal-alkyne complexes.]] |
[[File:VarietyPackAlkyneCmpx.svg|thumb|center|620px|Structures of various metal-alkyne complexes.]] |
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The coordination of alkynes to transition metals is similar to that of alkenes. The bonding is described by the [[Dewar–Chatt–Duncanson model]]. Upon complexation the C-C bond |
The coordination of alkynes to transition metals is similar to that of alkenes. The bonding is described by the [[Dewar–Chatt–Duncanson model]]. Upon complexation the C-C bond elongates and the alkynyl carbon bends away from 180º. For example, in the phenylpropyne complex Pt(PPh<sub>3</sub>)<sub>2</sub>(MeC<sub>2</sub>Ph), the C-C distance is 1.277(25) vs 1.20 Å for a typical alkyne. The C-C-C angle distorts 40° from linearity upon complexation.<ref>{{cite journal|first1=B. William |last1=Davies |last2=Payne|first2=N. C. |title=Studies on Metal-Acetylene Complexes: V. Crystal and Molecular Structure of Bis(triphenylphosphine)(1-phenylpropyne)platinum(0), [P(C<sub>6</sub>H<sub>5</sub>)<sub>3</sub>]<sub>2</sub>(C<sub>6</sub>H<sub>5</sub>CCCH<sub>3</sub>)Pt<sup>0</sup>|journal=J. Organomet. Chem.|year=1975| volume=99|page=315|doi=10.1016/S0022-328X(00)88462-4}}</ref> Because the bending induced by complexation, strained alkynes such as cycloheptyne and cyclooctyne are stabilized by complexation.<ref>{{cite journal|title=Metal Complexes of Small Cycloalkynes and Arynes |first1=Martin A. |last1=Bennett |first2=Heinz P. |last2=Schwemlein |journal=[[Angew. Chem. Int. Ed. Engl.]] |date=1989 |volume=28|issue=10 |pages=1296–1320|doi=10.1002/anie.198912961}}</ref> |
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The C≡C vibration of alkynes occurs near 2300 cm<sup>−1</sup> in the IR spectrum. This mode shifts upon complexation to around 1800 cm<sup>−1</sup>, indicating a weakening of the C-C bond. |
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===η<sup>2</sup>-coordination to a single metal center=== |
===η<sup>2</sup>-coordination to a single metal center=== |
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When bonded side-on to a single metal atom, an alkyne serves as a dihapto usually two-electron donor. For early metal complexes, e.g., Cp<sub>2</sub>Ti(C<sub>2</sub>R<sub>2</sub>), strong π-backbonding into one of the π* antibonding orbitals of the alkyne is indicated. This complex is described as a metallacyclopropene derivative of Ti(IV). For late transition metal complexes, e.g., Pt(PPh<sub>3</sub>)<sub>2</sub>(MeC<sub>2</sub>Ph), the π-backbonding is less prominent, and the complex is assigned oxidation state |
When bonded side-on to a single metal atom, an alkyne serves as a dihapto usually two-electron donor. For early metal complexes, e.g., Cp<sub>2</sub>Ti(C<sub>2</sub>R<sub>2</sub>), strong π-backbonding into one of the π* antibonding orbitals of the alkyne is indicated. This complex is described as a metallacyclopropene derivative of Ti(IV). For late transition metal complexes, e.g., Pt(PPh<sub>3</sub>)<sub>2</sub>(MeC<sub>2</sub>Ph), the π-backbonding is less prominent, and the complex is assigned oxidation state 0.<ref>Hill, A.F. ''Organotransition Metal Chemistry'', 2002, Royal Society of Chemistry, {{ISBN|0-471-28163-8}}.</ref><ref name=Crabtree>Crabtree, R. H. ''Comprehensive Organometallic Chemistry V'', 2009, John Wiley & Sons {{ISBN|978-0-470-25762-3}} {{Verify source|date=May 2015}}</ref> |
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In some complexes, the alkyne is classified as a four-electron donor. In these cases, both pairs of pi-electrons donate to the metal. This kind of bonding was first implicated in complexes of the type W(CO)(R<sub>2</sub>C<sub>2</sub>)<sub>3</sub>.<ref>Joseph L. Templeton |
In some complexes, the alkyne is classified as a four-electron donor. In these cases, both pairs of pi-electrons donate to the metal. This kind of bonding was first implicated in complexes of the type W(CO)(R<sub>2</sub>C<sub>2</sub>)<sub>3</sub>.<ref>{{cite journal|author=Joseph L. Templeton|title=Four-Electron Alkyne Ligands in Molybdenum(II) and Tungsten(II) Complexes|journal=Advances in Organometallic Chemistry'|year=1989|volume=29|page=1–100|doi=10.1016/S0065-3055(08)60352-4}}</ref> |
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===η<sup>2</sup>, η<sup>2</sup>-coordination bridging two metal centers=== |
===η<sup>2</sup>, η<sup>2</sup>-coordination bridging two metal centers=== |
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:C<sub>2</sub>R<sub>2</sub> + H<sub>2</sub> → ''cis''-C<sub>2</sub>R<sub>2</sub>H<sub>2</sub> |
:C<sub>2</sub>R<sub>2</sub> + H<sub>2</sub> → ''cis''-C<sub>2</sub>R<sub>2</sub>H<sub>2</sub> |
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This transformation is conducted on a large scale in refineries, which unintentionally produce acetylene during the production of ethylene. It is also useful in the preparation of fine chemicals. Semihydrogenation affords cis alkenes.<ref>{{cite journal |author1=Michaelides, I. N. |author2=Dixon, D. J.|title=Catalytic Stereoselective Semihydrogenation of Alkynes to E-Alkenes|journal=Angew. Chem. Int. Ed.|year=2013|volume=52|issue=3|pages=806–808|doi=10.1002/anie.201208120|pmid=23255528}}</ref> |
This transformation is conducted on a large scale in refineries, which unintentionally produce acetylene during the production of ethylene. It is also useful in the preparation of fine chemicals. [[Semihydrogenation]] affords cis alkenes.<ref>{{cite journal |author1=Michaelides, I. N. |author2=Dixon, D. J.|title=Catalytic Stereoselective Semihydrogenation of Alkynes to E-Alkenes|journal=Angew. Chem. Int. Ed.|year=2013|volume=52|issue=3|pages=806–808|doi=10.1002/anie.201208120|pmid=23255528|doi-access=free}}</ref> |
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Metal-alkyne complexes are also intermediates in the metal-catalyzed [[alkyne trimerisation|trimerization]] and tetramerizations. [[Cyclooctatetraene]] is produced from acetylene via the intermediacy of metal alkyne complexes. |
Metal-alkyne complexes are also intermediates in the metal-catalyzed [[alkyne trimerisation|trimerization]] and tetramerizations. [[Cyclooctatetraene]] is produced from acetylene via the intermediacy of metal alkyne complexes. Variants of this reaction are exploited for some syntheses of substituted [[pyridine]]s. |
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The [[Pauson–Khand reaction]] provides a route to cyclopentenones via the intermediacy of cobalt-alkyne complexes. |
The [[Pauson–Khand reaction]] provides a route to cyclopentenones via the intermediacy of cobalt-alkyne complexes. |
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[[Acrylic acid]] was once prepared by the [[hydrocarboxylation]] of acetylene:<ref name=Ullmann>{{ Ullmann | author = W. Bertleff |author2=M. Roeper |author3=X. Sava | title = Carbonylation | doi = 10.1002/14356007.a05_217}}</ref> |
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:C<sub>2</sub>H<sub>2</sub> + H<sub>2</sub>O + CO → H<sub>2</sub>C=CHCO<sub>2</sub>H |
:C<sub>2</sub>H<sub>2</sub> + H<sub>2</sub>O + CO → H<sub>2</sub>C=CHCO<sub>2</sub>H |
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With the shift away from coal-based (acetylene) to petroleum-based feedstocks (olefins), catalytic reactions with alkynes are not widely practiced industrially. |
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[[Polyacetylene]] has been produced using metal catalysis involving alkyne complexes. |
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:[[File:Ziegler natta scheme for polyacetylene.png|thumb|left|Ti-catalyzed polymerization of [[acetylene]], inspired by [[Ziegler–Natta catalysis]].]] |
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[[Cuprous chloride]] also catalyzes the [[Dimer (chemistry)|dimerization]] of [[acetylene]] to [[vinylacetylene]], once used as a precursor to various polymers such a [[neoprene]]. Mechanistic studies suggest that this reaction proceeds by insertion of acetylene into a copper(I) [[acetylide]] complex.<ref>{{cite journal |doi=10.1021/cr400357r |title=Catalytic Reactions of Acetylene: A Feedstock for the Chemical Industry Revisited |date=2014 |last1=Trotuş |first1=Ioan-Teodor |last2=Zimmermann |first2=Tobias |last3=Schüth |first3=Ferdi |journal=Chemical Reviews |volume=114 |issue=3 |pages=1761–1782 |pmid=24228942 |doi-access=free }}</ref> |
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{{clear}} |
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==References== |
==References== |
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<references /> |
<references /> |
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{{Organometallics}} |
{{Organometallics}}{{Coordination complexes}} |
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[[Category:Organometallic chemistry]] |
[[Category:Organometallic chemistry]] |
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[[Category:Transition metals]] |
[[Category:Transition metals]] |
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Latest revision as of 04:18, 13 May 2024
In organometallic chemistry, a transition metal alkyne complex is a coordination compound containing one or more alkyne ligands. Such compounds are intermediates in many catalytic reactions that convert alkynes to other organic products, e.g. hydrogenation and trimerization.[1]
Synthesis
[edit]Transition metal alkyne complexes are often formed by the displacement of labile ligands by the alkyne. For example, a variety of cobalt-alkyne complexes arise by the reaction of alkynes with dicobalt octacarbonyl.[2]
- Co2(CO)8 + R2C2 → (R2C2)Co2(CO)6 + 2 CO
Many alkyne complexes are produced by reduction of metal halides:[3]
- Cp2TiCl2 + Mg + Me3SiC≡CSiMe3 → Cp2Ti[(CSiMe3)2] + MgCl2
Structure and bonding
[edit]
The coordination of alkynes to transition metals is similar to that of alkenes. The bonding is described by the Dewar–Chatt–Duncanson model. Upon complexation the C-C bond elongates and the alkynyl carbon bends away from 180º. For example, in the phenylpropyne complex Pt(PPh3)2(MeC2Ph), the C-C distance is 1.277(25) vs 1.20 Å for a typical alkyne. The C-C-C angle distorts 40° from linearity upon complexation.[4] Because the bending induced by complexation, strained alkynes such as cycloheptyne and cyclooctyne are stabilized by complexation.[5]
The C≡C vibration of alkynes occurs near 2300 cm−1 in the IR spectrum. This mode shifts upon complexation to around 1800 cm−1, indicating a weakening of the C-C bond.
η2-coordination to a single metal center
[edit]When bonded side-on to a single metal atom, an alkyne serves as a dihapto usually two-electron donor. For early metal complexes, e.g., Cp2Ti(C2R2), strong π-backbonding into one of the π* antibonding orbitals of the alkyne is indicated. This complex is described as a metallacyclopropene derivative of Ti(IV). For late transition metal complexes, e.g., Pt(PPh3)2(MeC2Ph), the π-backbonding is less prominent, and the complex is assigned oxidation state 0.[6][7]
In some complexes, the alkyne is classified as a four-electron donor. In these cases, both pairs of pi-electrons donate to the metal. This kind of bonding was first implicated in complexes of the type W(CO)(R2C2)3.[8]
η2, η2-coordination bridging two metal centers
[edit]Because alkynes have two π bonds, alkynes can form stable complexes in which they bridge two metal centers. The alkyne donates a total of four electrons, with two electrons donated to each of the metals. And example of a complex with this bonding scheme is η2-diphenylacetylene-(hexacarbonyl)dicobalt(0).[7]
Benzyne complexes
[edit]Transition metal benzyne complexes represent a special case of alkyne complexes since the free benzynes are not stable in the absence of the metal.[9]
Applications
[edit]Metal alkyne complexes are intermediates in the semihydrogenation of alkynes to alkenes:
- C2R2 + H2 → cis-C2R2H2
This transformation is conducted on a large scale in refineries, which unintentionally produce acetylene during the production of ethylene. It is also useful in the preparation of fine chemicals. Semihydrogenation affords cis alkenes.[10]
Metal-alkyne complexes are also intermediates in the metal-catalyzed trimerization and tetramerizations. Cyclooctatetraene is produced from acetylene via the intermediacy of metal alkyne complexes. Variants of this reaction are exploited for some syntheses of substituted pyridines.
The Pauson–Khand reaction provides a route to cyclopentenones via the intermediacy of cobalt-alkyne complexes.
Acrylic acid was once prepared by the hydrocarboxylation of acetylene:[11]
- C2H2 + H2O + CO → H2C=CHCO2H
With the shift away from coal-based (acetylene) to petroleum-based feedstocks (olefins), catalytic reactions with alkynes are not widely practiced industrially.
Polyacetylene has been produced using metal catalysis involving alkyne complexes.
Ti-catalyzed polymerization of acetylene, inspired by Ziegler–Natta catalysis.
Cuprous chloride also catalyzes the dimerization of acetylene to vinylacetylene, once used as a precursor to various polymers such a neoprene. Mechanistic studies suggest that this reaction proceeds by insertion of acetylene into a copper(I) acetylide complex.[12]
References
[edit]- ^ Elschenbroich, C. ”Organometallics” 2006 Wiley-VCH: Weinheim. ISBN 3-527-29390-6.
- ^ Kemmitt, R. D. W.; Russell, D. R.; "Cobalt" in Comprehensive Organometallic Chemistry I; Abel, E.W.; Stone, F.G.A.; Wilkinson, G. eds., 1982, Pergamon Press, Oxford. ISBN 0-08-025269-9
- ^ Rosenthal, Uwe; Burlakov, Vladimir V.; Arndt, Perdita; Baumann, Wolfgang; Spannenberg, Anke (2003). "The Titanocene Complex of Bis(trimethylsilyl)acetylene: Synthesis, Structure, and Chemistry". Organometallics. 22 (5): 884–900. doi:10.1021/om0208570.
- ^ Davies, B. William; Payne, N. C. (1975). "Studies on Metal-Acetylene Complexes: V. Crystal and Molecular Structure of Bis(triphenylphosphine)(1-phenylpropyne)platinum(0), [P(C6H5)3]2(C6H5CCCH3)Pt0". J. Organomet. Chem. 99: 315. doi:10.1016/S0022-328X(00)88462-4.
- ^ Bennett, Martin A.; Schwemlein, Heinz P. (1989). "Metal Complexes of Small Cycloalkynes and Arynes". Angew. Chem. Int. Ed. Engl. 28 (10): 1296–1320. doi:10.1002/anie.198912961.
- ^ Hill, A.F. Organotransition Metal Chemistry, 2002, Royal Society of Chemistry, ISBN 0-471-28163-8.
- ^ a b Crabtree, R. H. Comprehensive Organometallic Chemistry V, 2009, John Wiley & Sons ISBN 978-0-470-25762-3 [verification needed]
- ^ Joseph L. Templeton (1989). "Four-Electron Alkyne Ligands in Molybdenum(II) and Tungsten(II) Complexes". Advances in Organometallic Chemistry'. 29: 1–100. doi:10.1016/S0065-3055(08)60352-4.
- ^ William M. Jones, Jerzy Klosin "Transition-Metal Complexes of Arynes, Strained Cyclic Alkynes, and Strained Cyclic Cumulenes" Advances in Organometallic Chemistry 1998, Volume 42, Pages 147–221. doi:10.1016/S0065-3055(08)60543-2
- ^ Michaelides, I. N.; Dixon, D. J. (2013). "Catalytic Stereoselective Semihydrogenation of Alkynes to E-Alkenes". Angew. Chem. Int. Ed. 52 (3): 806–808. doi:10.1002/anie.201208120. PMID 23255528.
- ^ W. Bertleff; M. Roeper; X. Sava. "Carbonylation". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a05_217. ISBN 978-3527306732.
- ^ Trotuş, Ioan-Teodor; Zimmermann, Tobias; Schüth, Ferdi (2014). "Catalytic Reactions of Acetylene: A Feedstock for the Chemical Industry Revisited". Chemical Reviews. 114 (3): 1761–1782. doi:10.1021/cr400357r. PMID 24228942.
