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1,1'-Bis(diphenylphosphino)ferrocene

{{chembox

| Name=1,1{{prime}}-Bis(diphenylphosphino){{SHY}}ferrocene

|Verifiedfields = correct

|Watchedfields = changed

|verifiedrevid = 477199791

|ImageFile = Dppfnew.png

|ImageSize = 150px

|ImageFile1 = Dppf-from-xtal-3D-balls.png

|ImageSize1 = 250px

|PIN = (Ferrocene-1,1{{prime}}-diyl)bis(diphenylphosphane)

|OtherNames = 1,1{{prime}}-Bis(diphenylphosphino)ferrocene, 1,1{{prime}}-ferrocenediylbis(diphenylphosphine), Dppf, 1,1{{prime}}-ferrocenebis(diphenylphosphine), 1,1{{prime}}-bis(diphenylphosphanyl)ferrocene

|Section1={{Chembox Identifiers

|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

|ChEBI_Ref = {{ebicite|correct|EBI}}

|ChEBI = 30743

|ChemSpiderID = 21865114

|EINECS = 640-119-0

|Gmelin = 24075

|InChI = 1/2C17H14P.Fe/c2*1-3-9-15(10-4-1)18(17- -13-7-8-14-17)16-11-5-2-6-12-16;/h2*1-14H;/q2*-1;+2

|InChIKey = HPXNTHKXCYMIJL-UHFFFAOYSA-N

|InChI1 = 1/2C17H14P.Fe/c2*1-3-9-15(10-4-1)18(17-13-7-8-14-17)16-11-5-2-6-12-16;/h2*1-14H;/rC34H28FeP2/c1-5-13-21(14-6-1)36(22-15-7-2-8-16-22)33-29-25-26-30(33)35(25,26,29,33)27-28(35)32(35)34(35,31(27)35)37(23-17-9-3-10-18-23)24-19-11-4-12-20-24/h1-20,25-32H

|InChIKey1 = HPXNTHKXCYMIJL-KDKHWAOJAX

|StdInChI_Ref = {{stdinchicite|correct|chemspider}}

|StdInChI = 1S/2C17H14P.Fe/c2*1-3-9-15(10-4-1)18(17-13-7-8-14-17)16-11-5-2-6-12-16;/h2*1-14H;

|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}

|StdInChIKey = HPXNTHKXCYMIJL-UHFFFAOYSA-N

|CASNo_Ref = {{cascite|correct|chemspider}}

|CASNo = 12150-46-8

|UNII_Ref = {{fdacite|correct|FDA}}

|UNII = L7Z23UWS3H

|PubChem = 635956

|SMILES1 = c1ccc(cc1)P(c2ccccc2)C34C5[Fe]3678912(C5C6C74)C3C8C9C1(C23)P(c1ccccc1)c1ccccc1

|SMILES2 = C1=CC=C(C=C1)P([C-]2C=CC=C2)C3=CC=CC=C3.C1=CC=C(C=C1)P([C-]2C=CC=C2)C3=CC=CC=C3.[Fe+2]

}}

|Section2={{Chembox Properties

|Formula = C{{sub|34}}H{{sub|28}}FeP{{sub|2}}

|MolarMass = 554.391

|MeltingPtC = 181 to 183

}}

|Section3={{Chembox Hazards

|MainHazards = Toxic

|GHSPictograms = {{GHS07}}{{GHS08}}

|GHSSignalWord = Warning

|HPhrases = {{H-phrases|302|312|315|319|332}}

}}

}}

1,1{{prime}}-Bis(diphenylphosphino)ferrocene, commonly abbreviated dppf, is an organophosphorus compound commonly used as a ligand in homogeneous catalysis. It contains a ferrocene moiety in its backbone, and is related to other bridged diphosphines such as 1,2-bis(diphenylphosphino)ethane (dppe).

Preparation

This compound is commercially available. It may be prepared by treating dilithioferrocene with chlorodiphenylphosphine:{{cite book | chapter = 3.15 The Use of Organolithium Reagents in the Preparation of Ferrocene Derivatives | author = Ian R. Butler | editor = J. Derek Woollins | year = 2010 | isbn = 978-3-527-32472-9 | title = Inorganic Experiments | pages = 175–179 | publisher = John Wiley & Sons | chapter-url = https://books.google.com/books?id=IlL_qLqj_nUC&pg=PA173 | chapter-format = Google Books excerpt}}

:Fe(C{{sub|5}}H{{sub|4}}Li){{sub|2}} + 2 ClPPh{{sub|2}} → Fe(C{{sub|5}}H{{sub|4}}PPh{{sub|2}}){{sub|2}} + 2 LiCl

The dilithiation of ferrocene is easily achieved with n-butyllithium in the presence of TMEDA. Many related ligands can be made in this way. The Fe center is typically not involved in the behavior of the ligand.

Reactions

Dppf readily forms metal complexes. The palladium derivative, (1,1'-Bis(diphenylphosphino)ferrocene)palladium(II) dichloride, which is popular for palladium-catalyzed coupling reactions, is prepared by treating dppf with the acetonitrile or benzonitrile adducts of palladium dichloride:{{cite journal | last1 = Nataro | first1 = Chip | last2 = Fosbenner | first2 = Stephanie M. | title = Synthesis and Characterization of Transition-Metal Complexes Containing 1,1{{prime}}-Bis(diphenylphosphino)ferrocene | journal = J. Chem. Educ. | volume = 86 | pages = 1412 | year = 2009 | doi = 10.1021/ed086p1412 | issue = 12| bibcode = 2009JChEd..86.1412N }} Substitution of the phenyl substituents in dppf leads to derivatives with modified donor-acceptor properties at the phosphorus atoms.{{cite journal | last1 = Dey | first1 = Subhayan | last2 = Pietschnig| first2 = Rudolf | title = Chemistry of sterically demanding dppf-analogs | journal = Coord. Chem. Rev. | volume = 437 | pages = 213850 | year = 2021 | doi = 10.1016/j.ccr.2021.213850 | doi-access = free}}

:dppf + PdCl{{sub|2}}(RCN){{sub|2}} → (dppf)PdCl{{sub|2}} + 2 RCN (RCN = acetonitrile or benzonitrile)

File:Dppf-PtCl2-from-xtal-3D-balls-B.png{{clear left}}

Another example of dppf in homogeneous catalysis is provided by the air- and moisture-stable Ni(II) precatalyst [(dppf)Ni(cinnamyl)Cl. It promotes Suzuki-Miyuara cross-coupling of heteroaryl boronic acids with nitrogen- and sulfur-containing heteroaryl halides.{{Cite journal |last1=Ge |first1=Shaozhong |last2=Hartwig |first2=John F. |date=2012-12-14 |title=Highly Reactive, Single-Component Nickel Catalyst Precursor for Suzuki–Miyuara Cross-Coupling of Heteroaryl Boronic Acids with Heteroaryl Halides |journal=Angewandte Chemie International Edition |language=en |volume=51 |issue=51 |pages=12837–12841 |doi=10.1002/anie.201207428 |pmc=3613336 |pmid=23136047}}

File:Hartwig synthesis.tif]

Another dppf-based catalyst is (dppf)Ni(o-tolyl)Cl, can be prepared from ligand exchange with (PPh3)2Ni(o-tolyl)Cl. It promotes the amination of aryl chlorides, sulfamates, mesylates, and triflates.{{Cite journal |last1=Park |first1=Nathaniel H. |last2=Teverovskiy |first2=Georgiy |last3=Buchwald |first3=Stephen L. |date=2014-01-03 |title=Development of an Air-Stable Nickel Precatalyst for the Amination of Aryl Chlorides, Sulfamates, Mesylates, and Triflates |journal=Organic Letters |volume=16 |issue=1 |pages=220–223 |doi=10.1021/ol403209k |pmc=3926134 |pmid=24283652}}

File:Buchwald Synthesis.tif

See also

References

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{{DEFAULTSORT:Bisdiphenylphosphinoferrocene, 1, 1'-}}

Category:Ferrocenes

Category:Tertiary phosphines

Category:Diphosphines