| 词条 | 1,2-Bis(diphenylphosphino)ethane |
| 释义 |
| Watchedfields = changed | verifiedrevid = 477203175 | Name = 1,2-Bis(diphenylphosphino)ethane | ImageFile = DPPE structure.svg | ImageName = | ImageFile1 = Dppe-from-xtal-2001-3D-balls.png | ImageName1 = dppe | IUPACName = Ethane-1,2-diylbis(diphenylphosphane) | OtherNames = 1,2-Bis(diphenylphosphino)ethane Diphos Dppe |Section1={{Chembox Identifiers | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | ChEBI_Ref = {{ebicite|correct|EBI}} | ChEBI = 30669 | ChemSpiderID = 66873 | PubChem = 74267 | EC_number = 216-769-2 | UNII = KL33QE52I4 | InChI = 1/C26H24P2/c1-5-13-23(14-6-1)27(24-15-7-2-8-16-24)21-22-28(25-17-9-3-10-18-25)26-19-11-4-12-20-26/h1-20H,21-22H2 | SMILES = P(c1ccccc1)(c2ccccc2)CCP(c3ccccc3)c4ccccc4 | InChIKey = QFMZQPDHXULLKC-UHFFFAOYAX | SMILES1 = c1ccc(cc1)P(CCP(c2ccccc2)c3ccccc3)c4ccccc4 | ChEMBL_Ref = {{ebicite|correct|EBI}} | ChEMBL = 68683 | Beilstein = 761261 | Gmelin = 9052 | StdInChI_Ref = {{stdinchicite|correct|chemspider}} | StdInChI = 1S/C26H24P2/c1-5-13-23(14-6-1)27(24-15-7-2-8-16-24)21-22-28(25-17-9-3-10-18-25)26-19-11-4-12-20-26/h1-20H,21-22H2 | StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} | StdInChIKey = QFMZQPDHXULLKC-UHFFFAOYSA-N | CASNo_Ref = {{cascite|correct|CAS}} | CASNo = 1663-45-2 |Section2={{Chembox Properties | Formula = C{{sub|26}}H{{sub|24}}P{{sub|2}} | MolarMass = 398.42 g/mol | MeltingPtC = 140 to 142 | MeltingPt_notes = |Section7 = {{Chembox Hazards | GHSPictograms = {{GHS07}}{{GHS09}} | GHSSignalWord = Warning | HPhrases = {{H-phrases|302|315|319|332|335|400|410}} | PPhrases = {{P-phrases|261|264|270|271|273|280|301+312|302+352|304+312|304+340|305+351+338|312|321|330|332+313|337+313|362|391|403+233|405|501}} }} }} 1,2-Bis(diphenylphosphino)ethane (dppe) is an organophosphorus compound with the formula (Ph{{sub|2}}PCH{{sub|2}}){{sub|2}} (Ph = phenyl). It is a commonly used bidentate ligand in coordination chemistry. It is a white solid that is soluble in organic solvents. PreparationThe preparation of dppe is by the alkylation of NaPPh{{sub|2}}:[1][2] P(C{{sub|6}}H{{sub|5}}){{sub|3}} + 2 Na → NaP(C{{sub|6}}H{{sub|5}}){{sub|2}} + NaC{{sub|6}}H{{sub|5}} NaP(C{{sub|6}}H{{sub|5}}){{sub|2}}, which is readily air-oxidized, is treated with 1,2-dichloroethane (ClCH{{sub|2}}CH{{sub|2}}Cl) to give dppe: 2 NaP(C{{sub|6}}H{{sub|5}}){{sub|2}} + ClCH{{sub|2}}CH{{sub|2}}Cl → (C{{sub|6}}H{{sub|5}}){{sub|2}}PCH{{sub|2}}CH{{sub|2}}P(C{{sub|6}}H{{sub|5}}){{sub|2}} + 2 NaCl ReactionsThe reduction of dppe by lithium to give PhHP(CH{{sub|2}}){{sub|2}}PHPh has been reported.[3] Ph{{sub|2}}P(CH{{sub|2}}){{sub|2}}PPh{{sub|2}} + 4 Li → PhLiP(CH{{sub|2}}){{sub|2}}PLiPh + 2 PhLi Hydrolysis gives the bis(secondaryphosphine): PhLiP(CH{{sub|2}}){{sub|2}}PLiPh + 2 PhLi + 4H{{sub|2}}O → PhHP(CH{{sub|2}}){{sub|2}}PHPh + 4 LiOH + 2 C{{sub|6}}H{{sub|6}} Treatment of dppe with conventional oxidants such as hydrogen peroxide (H{{sub|2}}O{{sub|2}}), aqueous bromine (Br{{sub|2}}), etc., produces dppeO in low yield (e.g., 13%) as a result of non-selective oxidation.[4] Selective mono-oxidation of dppe can be achieved by reaction with PhCH{{sub|2}}Br to give dppeO. {{NumBlk|:|Ph{{sub|2}}P(CH{{sub|2}}){{sub|2}}PPh{{sub|2}} + PhCH{{sub|2}}Br → Ph{{sub|2}}P(CH{{sub|2}}){{sub|2}}PPh{{sub|2}}(CH{{sub|2}}Ph){{sup|+}}Br{{sup|−}}|{{EquationRef|2.3.}}}}{{NumBlk|:|Ph{{sub|2}}P(CH{{sub|2}}){{sub|2}}PPh{{sub|2}}(CH{{sub|2}}Ph){{sup|+}}Br{{sup|−}} + NaOH + H{{sub|2}}O → Ph{{sub|2}}P(CH{{sub|2}}){{sub|2}}P(O)Ph{{sub|2}}|{{EquationRef|2.4.}}}}Hydrogenation of dppe gives the ligand bis(dicyclohexylphosphino)ethane. Coordination complexesMany coordination complexes of dppe are known, and some are used as homogeneous catalysts. Dppe is almost invariably chelating, although there are examples of monodentate (e.g., W(CO){{sub|5}}(dppe)) and of bridging behavior.[5] The natural bite angle is 86°.[6] Related compounds
References1. ^{{cite journal | journal = J. Chem. Soc. | year = 1962 | pages = 1490–1494 | doi = 10.1039/JR9620001490 | title = 283. The preparation of di- and tri-tertiary phosphines | author = W. Hewertson and H. R. Watson}} {{DEFAULTSORT:Bis(diphenylphosphino)ethane}}2. ^Girolami, G.; Rauchfuss, T.; Angelici, R. Synthesis and Technique in Inorganic Chemistry, 3rd ed.; University Science Books: Sausalito, CA, 1999; pp. 85-92. {{ISBN|0-935702-48-2}} 3. ^{{cite journal | author = Dogan, J. |author2= Schulte, J.B.|author3= Swiegers, G.F.|author4= Wild, S.B. | year = 2000 | title = Mechanism of Phosphorus-Carbon Bond Cleavage by Lithium in Tertiary Phosphines. An Optimized Synthesis of 1, 2-Bis (phenylphosphino) ethane | journal = J. Org. Chem. | volume = 65 | issue = 4 | pages = 951–957 | doi = 10.1021/jo9907336}} 4. ^Encyclopedia of Reagents for Organic Synthesis 2001 John Wiley & Sons, Ltd 5. ^Cotton, F.A.; Wilkinson, G. Advanced Inorganic Chemistry: A Comprehensive Text, 4th ed.; Wiley-Interscience Publications: New York, NY, 1980; p.246. {{ISBN|0-471-02775-8}} 6. ^{{cite journal |last1=Birkholz (née Gensow) |first1=Mandy-Nicole |last2=Freixa |first2=Zoraida |last3=van Leeuwen |first3=Piet W. N. M. |title=Bite angle effects of diphosphines in C–C and C–X bond forming cross coupling reactions |journal=Chemical Society Reviews |date=2009 |volume=38 |issue=4 |pages=1099 |doi=10.1039/B806211K}} 3 : Chelating agents|Bisphosphanes|Phenyl compounds |
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