User:Indiacox/Dicarbonyldi-μ-chlorodichlorodiplatinum

Trans-Dicarbonyldi-μ-chlorodichlorodiplatinum is the first ever isolated metal-carbonyl complex. It was first synthesized by Paul Schützenberger in 1868.^[1] This discovery of ${\ce {[Pt(CO)Cl2]2}}$ opened the door for the exploration of metal-carbonyl complexes and represents a significant breakthrough in the field of organometallic chemistry.^[1] Though ${\ce {[Pt(CO)Cl2]2}}$ itself is not used in industry, metal carbonyls are an important class of catalysts for a wide range of industrial processes including hydroformylation amongst others.^[2] As such, the discovery of ${\ce {[Pt(CO)Cl2]2}}$ was an important milestone both in the synthesis of organometallic compounds and in the development of many important catalysts widely used today.

Structure and Characterization

It should be noted that dicarbonyldi-μ-chlorodichlorodiplatinum has both cis and trans isomers. Unless noted otherwise, ${\ce {[Pt(CO)Cl2]2}}$ in this article specifically refers to the trans isomer.

Crystal Structure

The crystal structure of ${\ce {[Pt(CO)Cl2]2}}$ has been obtained. ${\ce {[Pt(CO)Cl2]2}}$ can be roughly thought of as two square planar ${\ce {Pt(CO)Cl3}}$ centers, but the complex does not perfectly align with that model; the two platinum centers deviate from the square planar geometry of ${\ce {Pt(Cl)3CO}}$ monomers. The μ-chloro ligands and the ${\ce {CO}}$ ligand on each ${\ce {Pt}}$ center are coplanar, but the terminal ${\ce {Cl}}$ on both ${\ce {Pt}}$ centers is 0.228 Å out of plane, giving the complex overall ${\ce {C2}}$ symmetry.^[3] Additionally, the bridging chlorines are not equally shared between the two ${\ce {Pt}}$ centers.^[3]

Spectroscopic Characterization

IR spectroscopy and NMR have also both been used to characterize ${\ce {[Pt(CO)Cl2]2}}$ . The CO stretching frequency for ${\ce {[Pt(CO)Cl2]2}}$ is 2139 cm^-1 in DCM (the C-O stretching frequency has also been measured in thionyl chloride, cyclohexane and benzene, toluene and n-heptane).^[4] ${\ce {^{195}Pt}}$ NMR reveals two ${\ce {Pt}}$ peaks for ${\ce {[Pt(CO)Cl2]2}}$ (at 1507 and 1511 ppm) in thionyl chloride. This is believed to be due to the formation of two distinct ${\ce {Pt}}$ dimers in solution (where solvation effects cause slight changes in ${\ce {Pt}}$ chemical shift) or stacking of dimers in solution giving rise to distinct ${\ce {Pt}}$ shifts.^[5] ${\ce {^{13}C}}$ NMR reveals a 139.9 shift for the carbonyl carbons with a ${\ce {^{195}Pt ^{13}C}}$ coupling constant of 1958.8Hz.^[6]

Synthesis

Schützenberger's discovery of ${\ce {[Pt(CO)Cl2]2}}$

Compounds synthesized by Schutzenberger from ${\ce {Pt}}$ sponge, ${\ce {Cl2}}$ and ${\ce {CO}}$ . ${\ce {[PtCl2(CO)]2}}$ is favored at high temperatures

Schützenberger first synthesized ${\ce {[Pt(CO)Cl2]2}}$ in 1868.^[1]^[7] The complex was sourced from ${\ce {Pt}}$ black and ${\ce {CO}}$ and ${\ce {Cl2}}$ gases, but there are conflicting reports on whether he flowed a mixture of the gasses over platinum black or first formed ${\ce {PtCl2}}$ and subsequently exposed the compound to ${\ce {CO}}$ .^[3]^[7] However, Schützenberger's isolated product is consistently reported to be a volatile yellow solid. Schützenberger also observed that performing the reaction at different temperatures yields compounds with different melting points.^[7] Based on this observation, Schützenberger identified that the composition of the platinum complex formed under these conditionsis determined by the temperature at which the reaction proceeds. ${\ce {Pt(CO)2Cl2}}$ is formed at a narrow temperature range with this procedure, but the diplatinum complex (and liberation of two ${\ce {CO}}$ equivalents) is favored at higher temperatures.^[7]

More Recent Syntheses

More recently, ${\ce {[Pt(CO)Cl2]2}}$ has been accessed from other platinum complexes. Dell'Amico et al. reported the formation of ${\ce {[Pt(CO)Cl2]2}}$ from the dimerization of trans- ${\ce {[PtCI2(NCEt)(CO)]}}$ with the production of 2 equivalents of ${\ce {EtCN}}$ as a byproduct.^[8] To obtain ${\ce {[Pt(CO)Cl2]2}}$ , cis- ${\ce {[PtCI2(NCEt)(CO)]}}$ is dissolved in dry mesitylene.^[8] The solution is then heated, allowing the solvent to evaporate. ${\ce {^{195}Pt}}$ NMR analysis of the resulting solid reveals a mixture of of trans- ${\ce {[PtCI2(NCEt)(CO)]}}$ and ${\ce {[Pt(CO)Cl2]2}}$ .^[8] Repeating this dissolution/evaporation procedure yields an orange residue showing complete conversion to ${\ce {[Pt(CO)Cl2]2}}$ .^[8]

Synthesis of ${\ce {[Pt(CO)Cl2]2}}$ from ${\ce {Pt(CO)(NCEt)Cl2}}$ .

Solution phase synthesis of ${\ce {[Pt(CO)Cl2]2}}$ from ${\ce {PtCl4^{2-}}}$ .

Alternatively, ${\ce {[Pt(CO)Cl2]2}}$ has been prepared from

${\ce {Pt(CO)Cl3^-}}$ .^[3] ${\ce {Pt(CO)Cl3^-}}$ can be generated in chlorinated solvents by treating ${\ce {PtCl4^{2-}}}$ with ${\ce {AlCl3}}$ under a ${\ce {CO}}$ atmosphere.^[3] ${\ce {Pt(CO)Cl3^-}}$ can also be accessed by allowing ${\ce {PtCl4^{2-}}}$ to equilibrate under a ${\ce {CO}}$ atmosphere at room temperature, but this equilibration occurs over the course of approximately 40 hours.^[3] ${\ce {[Pt(CO)Cl2]2}}$ can then be generated from ${\ce {Pt(CO)Cl3^-}}$ by treatment with ${\ce {AlCl3}}$ under a nitrogen atmosphere. Interestingly, treating ${\ce {Pt(CO)Cl3^-}}$ with ${\ce {AlCl3}}$ under a ${\ce {CO}}$ atmosphere, trans- ${\ce {Pt(CO)2Cl2}}$ is formed instead.^[3]

Reactivity

Dissociation of ${\ce {[Pt(CO)Cl2]2}}$ into ${\ce {Pt(CO)2Cl2}}$ .

Olefin addition to ${\ce {[PtCl2(CO)]2}}$ .

${\ce {[Pt(CO)Cl2]2}}$ can dissociate into mono-platinum complexes. By dissolving ${\ce {[Pt(CO)Cl2]2}}$ in thionyl chloride and exposing the solution to atmospheric pressure of ${\ce {CO}}$ at room temperature, ${\ce {Pt(CO)2Cl2}}$ is formed.^[5] Interestingly, trans- ${\ce {Pt(CO)2Cl2}}$ is observed shortly after exposure to ${\ce {CO}}$ , but after allowing the reaction to proceed for 24 hours, the cis isomer is exclusively observed.^[5] Trans- ${\ce {Pt(CO)2Cl2}}$ can also be isolated from ${\ce {[Pt(CO)Cl2]2}}$ by performing the reaction at -80°C. This reaction is observed to be complete after 10 hours. Trans- ${\ce {Pt(CO)2Cl2}}$ is stable at -80°C, but rapidly converts to the cis isomer at room temperature.^[5] Alternatively, olefin substitution can cause the dissociation of the diplatinum complex.^[9] ${\ce {[Pt(CO)Cl2]2}}$ and an olefin (cyclohexene, ethylene or propylene) can be combined in toluene, causing the dissociation of the diplatinum complex to form two equivalents of cis- ${\ce {PtCl2(CO)(olefin)}}$ .^[9]

${\ce {[Pt(CO)Cl2]2}}$ has also been explored as a molecular precursor for loading platinum onto silica (which has been subsequently used to hydrogenate cyclohexene on a laboratory scale).^[10] To do so, dry silica is treated with ${\ce {[Pt(CO)Cl2]2}}$ in toluene at room temperature under a nitrogen atmosphere.^[10] The ${\ce {Pt}}$ containing fragments appear to migrate to the surface of the silica based on the orange color of the material after treatment. Authors attribute this color change to adsorption of a ${\ce {Pt}}$ center onto the ${\ce {SiO2}}$ surface followed by cleavage of the μ-chloro linkages to form surface bound ${\ce {PtCl2(CO)}}$ species.^[10] The treated ${\ce {SiO2}}$ particles were then recovered by filtration and exposed to water vapor at 40°C to liberate ${\ce {CO2}}$ and ${\ce {HCl}}$ , leaving metallic ${\ce {Pt}}$ loaded on silica.^[10]

Overall reaction for ${\ce {Pt}}$ loading onto silica nanoparticles from ${\ce {[PtCl2(CO)]2}}$ .

${\ce {[Pt(CO)Cl2]2}}$ has also been used as a starting material for the formation of more complicated platinum containing complexes. Panuzi et al. report the formation of a diplatinum complex formed by reacting a functionalized xanthene with ${\ce {[Pt(CO)Cl2]2}}$ (shown in the figure below). To synthesize the bidentate xanthene ligand, 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethylxanthene and excess ${\ce {CuCN}}$ are refluxed in dry quinoline for 24 hours. The resulting solid is then washed with diethyl ether and extracted into chloroform. The solid is then purified on a silica column with a 40:1 DCM:methanol eluent (40% yield). To form the platinum complex, the synthesized ligand is combined with excess ${\ce {[Pt(CO)Cl2]2}}$ in toluene. The mixture was allowed to stand overnight at 5°C, where yellow crystals formed. These crystals were then isolated and washed with dry toluene, yielding the pure diplatinum xanthene complex.^[11]

Synthesis of other complexes from ${\ce {[Pt(CO)Cl2]2}}$ .

Catalytic hydrochlorination of cyclohexene.

${\ce {[Pt(CO)Cl2]2}}$ has also been reported as a pre-catalyst for the ${\ce {Pt}}$ catalyzed hydrochlorination of cyclohexene. ^[9] Alper et al. report the reaction of ${\ce {Pt(CO)Cl2(C6H10)}}$ and ${\ce {HCl}}$ to form ${\ce {[Pt(CO)Cl2]2}}$ and liberate ${\ce {C6H11Cl}}$ . ${\ce {[Pt(CO)Cl2]2}}$ can then be reacted with two equivalents of cyclohexene to regenerate ${\ce {Pt(CO)Cl2(C6H10)}}$ .^[9] The overall reaction from these two steps is the catalyzed chlorination of cyclohexene.^[9]

References

^ ^a ^b ^c Elschenbroich, Christoph (2006). Organometallics (3rd ed.). Weinheim: Wiley-VCH. ISBN 3-527-29390-6. OCLC 64305455.
^ Comprehensive organometallic chemistry III. D. M. P. Mingos, Robert H. Crabtree (1st ed.). Amsterdam: Elsevier. 2007. ISBN 0-08-052350-1. OCLC 228076728.{{cite book}}: CS1 maint: others (link)
^ ^a ^b ^c ^d ^e ^f ^g Bagnoli, Franco; Belli Dell'Amico, Daniela; Calderazzo, Fausto; Englert, Ulli; Marchetti, Fabio; Merigo, Alessandra; Ramello, Stefano (2001). "Halo-carbonyl complexes of platinum(II) and palladium(II)". Journal of Organometallic Chemistry. 622 (1): 180–189. doi:10.1016/S0022-328X(00)00947-5. ISSN 0022-328X.
^ Calderazzo, Fausto; Dell'Amico, Daniela Belli (1981). "Syntheses of carbonyl halides of late transition elements in thionyl chloride as solvent. Carbonyl complexes of palladium(II)". Inorganic Chemistry. 20 (4): 1310–1312. doi:10.1021/ic50218a072. ISSN 0020-1669.
^ ^a ^b ^c ^d Belli Dell'Amico, Daniela; Calderazzo, Fausto; Veracini, Carlo Alberto; Zandona, Nicola (1984). "Comparison between carbonyl derivatives of palladium and those of nickel and platinum". Inorganic Chemistry. 23 (19): 3030–3033. doi:10.1021/ic00187a027. ISSN 0020-1669.
^ Andreini, Bianca Patrizia; Belli Dell'Amico, Daniela; Calderazzo, Fausto; Venturi, Maria Giovanna; Pelizzi, Giancarlo; Serge, Annalaura (1988). "Carbonyl complexes of noble metals with halide ligands". Journal of Organometallic Chemistry. 354 (3): 357–368. doi:10.1016/0022-328X(88)80661-2.
^ ^a ^b ^c ^d Wisniak, Jaime (2015). "Paul Schützenberger". Educación Química (in Spanish). 26 (1): 57–65. doi:10.1016/S0187-893X(15)72100-2.
^ ^a ^b ^c ^d Dell'Amico, Daniela Belli; Labella, Luca; Marchetti, Fabio; Samaritani, Simona (2012). "A convenient route to dinuclear chloro-bridged platinum( ii ) derivatives vianitrile complexes". Dalton Trans. 41 (4): 1389–1396. doi:10.1039/C1DT11709B. ISSN 1477-9226.
^ ^a ^b ^c ^d ^e Alper, Howard; Huang, Yujin; Belli Dell'Amico, Daniela; Calderazzo, Fausto; Pasqualetti, Nicola; Veracini, Carlo Alberto (1991). "Synthesis of carbonyl-olefin complexes of platinum(II), PtX2(CO)(olefin), and the catalytic hydrochlorination of olefins". Organometallics. 10 (6): 1665–1671. doi:10.1021/om00052a010. ISSN 0276-7333.
^ ^a ^b ^c ^d Armelao, Lidia; Belli Dell’Amico, Daniela; Braglia, Roberto; Calderazzo, Fausto; Garbassi, Fabio; Marra, Gianluigi; Merigo, Alessandra (2009). "Loading silica with metals (palladium or platinum) under mild conditions by using well-defined molecular precursors". Dalton Transactions (28): 5559. doi:10.1039/b903655e. ISSN 1477-9226.
^ Panunzi, Achille; Giordano, Federico; Orabona, Ida; Ruffo, Francesco (2005). "Binuclear platinum complexes of 4,5-disubstituted xanthenes". Inorganica Chimica Acta. 358 (4): 1217–1224. doi:10.1016/j.ica.2004.11.034.

[:0-1] Elschenbroich, Christoph (2006). Organometallics (3rd ed.). Weinheim: Wiley-VCH. ISBN 3-527-29390-6. OCLC 64305455.

[2] Comprehensive organometallic chemistry III. D. M. P. Mingos, Robert H. Crabtree (1st ed.). Amsterdam: Elsevier. 2007. ISBN 0-08-052350-1. OCLC 228076728.{{cite book}}: CS1 maint: others (link)

[:1-3] ^ ^a ^b ^c ^d ^e ^f ^g Bagnoli, Franco; Belli Dell'Amico, Daniela; Calderazzo, Fausto; Englert, Ulli; Marchetti, Fabio; Merigo, Alessandra; Ramello, Stefano (2001). "Halo-carbonyl complexes of platinum(II) and palladium(II)". Journal of Organometallic Chemistry. 622 (1): 180–189. doi:10.1016/S0022-328X(00)00947-5. ISSN 0022-328X.

[4] Calderazzo, Fausto; Dell'Amico, Daniela Belli (1981). "Syntheses of carbonyl halides of late transition elements in thionyl chloride as solvent. Carbonyl complexes of palladium(II)". Inorganic Chemistry. 20 (4): 1310–1312. doi:10.1021/ic50218a072. ISSN 0020-1669.

[:2-5] Belli Dell'Amico, Daniela; Calderazzo, Fausto; Veracini, Carlo Alberto; Zandona, Nicola (1984). "Comparison between carbonyl derivatives of palladium and those of nickel and platinum". Inorganic Chemistry. 23 (19): 3030–3033. doi:10.1021/ic00187a027. ISSN 0020-1669.

[6] Andreini, Bianca Patrizia; Belli Dell'Amico, Daniela; Calderazzo, Fausto; Venturi, Maria Giovanna; Pelizzi, Giancarlo; Serge, Annalaura (1988). "Carbonyl complexes of noble metals with halide ligands". Journal of Organometallic Chemistry. 354 (3): 357–368. doi:10.1016/0022-328X(88)80661-2.

[:3-7] Wisniak, Jaime (2015). "Paul Schützenberger". Educación Química (in Spanish). 26 (1): 57–65. doi:10.1016/S0187-893X(15)72100-2.

[:4-8] Dell'Amico, Daniela Belli; Labella, Luca; Marchetti, Fabio; Samaritani, Simona (2012). "A convenient route to dinuclear chloro-bridged platinum( ii ) derivatives vianitrile complexes". Dalton Trans. 41 (4): 1389–1396. doi:10.1039/C1DT11709B. ISSN 1477-9226.

[:6-9] Alper, Howard; Huang, Yujin; Belli Dell'Amico, Daniela; Calderazzo, Fausto; Pasqualetti, Nicola; Veracini, Carlo Alberto (1991). "Synthesis of carbonyl-olefin complexes of platinum(II), PtX2(CO)(olefin), and the catalytic hydrochlorination of olefins". Organometallics. 10 (6): 1665–1671. doi:10.1021/om00052a010. ISSN 0276-7333.

[:5-10] Armelao, Lidia; Belli Dell’Amico, Daniela; Braglia, Roberto; Calderazzo, Fausto; Garbassi, Fabio; Marra, Gianluigi; Merigo, Alessandra (2009). "Loading silica with metals (palladium or platinum) under mild conditions by using well-defined molecular precursors". Dalton Transactions (28): 5559. doi:10.1039/b903655e. ISSN 1477-9226.

[11] Panunzi, Achille; Giordano, Federico; Orabona, Ida; Ruffo, Francesco (2005). "Binuclear platinum complexes of 4,5-disubstituted xanthenes". Inorganica Chimica Acta. 358 (4): 1217–1224. doi:10.1016/j.ica.2004.11.034.

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