Karstedt's catalyst

Karstedt's catalyst
Identifiers
CAS Number	68478-92-2;
3D model (JSmol)	Interactive image;
ChemSpider	9135105;
EC Number	270-844-4;
PubChem CID	10959889;
UN number	1307
	InChI InChI=1S/C8H18OSi2.Pt/c1-7-10(3,4)9-11(5,6)8-2;/h7-8H,1-2H2,3-6H3; Key: RCNRJBWHLARWRP-UHFFFAOYSA-N;
	SMILES C[Si](C)(C=C)O[Si](C)(C)C=C.[Pt];
Properties
Chemical formula	C24H54O3Pt2Si6
Molar mass	949.4 g/mol
Appearance	colorless solid
Density	1.74 g/cm3
Melting point	12 to 13 °C (54 to 55 °F; 285 to 286 K)
Boiling point	139 °C (282 °F; 412 K)
Solubility in water	insoluble
Hazards
GHS pictograms
GHS Signal word	Danger
GHS hazard statements	H226, H304, H312, H315, H319, H332, H335, H373
GHS precautionary statements	P210, P260, P280, P301+310, P305+351+338, P370+378
Flash point	86
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	Infobox references

Karstedt's catalyst is an organoplatinum compound derived from divinyl-containing disiloxane. This coordination complex is widely used in hydrosilylation catalysis. It is a colorless solid that is generally assumed to be a mixture of related Pt(0) alkene complexes.[1][2] The catalyst is named after Bruce D. Karstedt, who developed it in the early 1970s while working for General Electric.[3]

Applications

Carbon-silicon bonds are often generated via hydrosilylation of alkenes. This reaction has very important applications to industry. While it is favorable thermodynamically, hydrosilylation does not proceed in the absence of a catalyst, such as Karstedt's catalyst. The catalyst is produced by treatment of chloroplatinic acid by the divinyltetramethyldisiloxane.[4] [5]

The catalyst can also be used in a reductive amination reaction between a carboxylic acid and an amine with phenylsilane as the reducing agent.[6]

Structure and bonding

The oxidation state of the platinum is 0. Using X-ray crystallography, the structure of Pt₂[(Me₂SiCH=CH₂)₂O]₃ has been confirmed. Each Pt(0) center is surrounded by three alkene ligands provided by three 1,1,3,3-tetramethyl-1,3-divinyldisiloxane ligands. The Pt center and six coordinated carbon atoms are approximately coplanar, as found for simpler complexes such as Pt(C₂H₄)₃.[7]

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References

Lewis, Larry N.; Stein, Judith; Gao, Yan; Colborn, Robert E.; Hutchins, Gudrun (1997). "Platinum catalysts used in the silicones industry" (PDF). Platinum Metals Review. 41 (2): 66–74.
Stein, Judith; Lewis, L. N.; Gao, Y.; Scott, R. A. "In Situ Determination of the Active Catalyst in Hydrosilylation Reactions Using Highly Reactive Pt(0) Catalyst Precursors". Journal of the American Chemical Society. 121 (15): 3693–3703. doi:10.1021/ja9825377.
US Patent 3775452, Bruce D. Karstedt, "Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes", published 1973-11-27, assigned to General Electric
Richard T. Beresis, Jason S. Solomon, Michael G. Yang, Nareshkumar F. Jain, James S. Panek (1998). "Synthesis of Chiral (E)-Crotylsilanes: [3R- and 3S-]-(4E)-Methyl 3-(Dimethylphenylsilyl)-4-Hexenoate". Organic Syntheses. 75: 78. doi:10.15227/orgsyn.075.0078.CS1 maint: multiple names: authors list (link)
Kohei Tamao, Yoshiki Nakagawa, Yoshihiko Ito (1996). "Regio- and Stereoselective Intramolecular Hydrosilylation of a-hydroxy Enol Ethers: 2,3-syn-2-Methoxymethoxy-1,3-Nonanediol". Organic Syntheses. 73: 94. doi:10.15227/orgsyn.073.0094.CS1 maint: uses authors parameter (link)
Sorribes, Iván; Junge, Kathrin; Beller, Matthias (29 September 2014). "Direct Catalytic N-Alkylation of Amines with Carboxylic Acids". Journal of the American Chemical Society. 136 (40): 14314–14319. doi:10.1021/ja5093612. PMID 25230096.
Hitchcock, Peter B.; Lappert, Michael F.; Warhurst, Nicholas J. W. "Synthesis and Structure of arac-Tris(divinyldisiloxane) diplatinum(0) Complex and its Reaction with Maleic Anhydride". Angewandte Chemie International Edition in English. 30 (4): 438–440. doi:10.1002/anie.199104381.

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[1] Lewis, Larry N.; Stein, Judith; Gao, Yan; Colborn, Robert E.; Hutchins, Gudrun (1997). "Platinum catalysts used in the silicones industry" (PDF). Platinum Metals Review. 41 (2): 66–74.

[2] Stein, Judith; Lewis, L. N.; Gao, Y.; Scott, R. A. "In Situ Determination of the Active Catalyst in Hydrosilylation Reactions Using Highly Reactive Pt(0) Catalyst Precursors". Journal of the American Chemical Society. 121 (15): 3693–3703. doi:10.1021/ja9825377.

[3] US Patent 3775452, Bruce D. Karstedt, "Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes", published 1973-11-27, assigned to General Electric

[4] Richard T. Beresis, Jason S. Solomon, Michael G. Yang, Nareshkumar F. Jain, James S. Panek (1998). "Synthesis of Chiral (E)-Crotylsilanes: [3R- and 3S-]-(4E)-Methyl 3-(Dimethylphenylsilyl)-4-Hexenoate". Organic Syntheses. 75: 78. doi:10.15227/orgsyn.075.0078.CS1 maint: multiple names: authors list (link)

[5] Kohei Tamao, Yoshiki Nakagawa, Yoshihiko Ito (1996). "Regio- and Stereoselective Intramolecular Hydrosilylation of a-hydroxy Enol Ethers: 2,3-syn-2-Methoxymethoxy-1,3-Nonanediol". Organic Syntheses. 73: 94. doi:10.15227/orgsyn.073.0094.CS1 maint: uses authors parameter (link)

[6] Sorribes, Iván; Junge, Kathrin; Beller, Matthias (29 September 2014). "Direct Catalytic N-Alkylation of Amines with Carboxylic Acids". Journal of the American Chemical Society. 136 (40): 14314–14319. doi:10.1021/ja5093612. PMID 25230096.

[7] Hitchcock, Peter B.; Lappert, Michael F.; Warhurst, Nicholas J. W. "Synthesis and Structure of arac-Tris(divinyldisiloxane) diplatinum(0) Complex and its Reaction with Maleic Anhydride". Angewandte Chemie International Edition in English. 30 (4): 438–440. doi:10.1002/anie.199104381.