2071-20-7

Basic information

• Product Name: Bis(diphenylphosphino)methane
• Synonyms: METHYLENEBIS(DIPHENYLPHOSPHINE);AURORA KA-1146;BIS(DIPHENYLPHOSPHINE)METHANE;BIS(DIPHENYLPHOSPHINO)METHANE;DPM;[(1,1-DIPHENYLPHOSPHINO)METHYL](DIPHENYL)PHOSPHINE;Dppm~Methylenebis(diphenylphosphine);Bis(diphenylphosphino)methane,97%
• CAS NO: 2071-20-7
• Molecular Formula: C₂₅H₂₂P₂
• Molecular Weight: 384.39
• EINECS: 218-194-2
• Product Categories: Phosphines;Ligand;Phosphine Ligands;Synthetic Organic Chemistry;organophosphine ligand;Achiral Phosphine;Aryl Phosphine
• Mol File: 2071-20-7.mol

Chemical Properties

• Melting Point: 118-119 °C(lit.)
• Boiling Point: 497.2 °C at 760 mmHg
• Flash Point: 270.2 °C
• Appearance: Almost white/Fine Crystalline Powder
• Vapor Pressure: 1.55E-09mmHg at 25°C
• Storage Temp.: Store below +30°C.
• Water Solubility: Insoluble in water.
• Sensitive: Air Sensitive
• BRN: 758760
• CAS DataBase Reference: Bis(diphenylphosphino)methane(CAS DataBase Reference)
• NIST Chemistry Reference: Bis(diphenylphosphino)methane(2071-20-7)
• EPA Substance Registry System: Bis(diphenylphosphino)methane(2071-20-7)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 22-24/25-37/39-26
• WGK Germany: 3
• F: 10-23
• TSCA: No
• Hazardous Substances Data: 2071-20-7(Hazardous Substances Data)

Usage

Uses

Used in Suzuki Reaction:
Bis(diphenylphosphino)methane is used as a catalyst in the Suzuki reaction, a widely used cross-coupling reaction in organic synthesis. It facilitates the formation of carbon-carbon bonds between an aryl or vinyl halide and a boronic acid or ester, leading to the formation of biaryl compounds.
Used in Organic Synthesis:
Bis(diphenylphosphino)methane is used as an organic synthesis catalyst, particularly in palladium-catalyzed reactions. It enhances the efficiency and selectivity of various organic reactions, including cross-coupling, cyclization, and carbonylation reactions.
Used in Flavor and Fragrance Industry:
Bis(diphenylphosphino)methane is used as an intermediate in the synthesis of flavor and fragrance compounds. Its unique chemical properties allow for the creation of complex and diverse molecules with desirable sensory properties.

InChI:InChI=1/C25H22P2/c1-5-13-22(14-6-1)26(23-15-7-2-8-16-23)21-27(24-17-9-3-10-18-24)25-19-11-4-12-20-25/h1-20H,21H2

Synthetic route

methanol (67-56-1) + methylenebis(diphenylphosphane)-borane(1:2) (24442-15-7) → Trimethyl borate (121-43-7) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
In toluene at 100℃; Inert atmosphere;	A n/a B 100%

diphenylphosphane (829-85-6) + 1,1-dibromomethane (74-95-3) → bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
With cesium hydroxide; 4 Angstroem MS In N,N-dimethyl-formamide at 23℃; for 16h;	95%
With cesium hydroxide; 4 A molecular sieve In N,N-dimethyl-formamide at 23℃; for 16h;	95%
Stage #1: diphenylphosphane With cesiumhydroxide monohydrate In N,N-dimethyl-formamide at 20℃; for 1h; Molecular sieve; Inert atmosphere; Stage #2: 1,2-dibromomethane In N,N-dimethyl-formamide at 20℃; for 16h; Inert atmosphere; Molecular sieve;	95%

ethanol (64-17-5) + methylenebis(diphenylphosphane)-borane(1:2) (24442-15-7) → triethyl borate (150-46-9) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
Inert atmosphere; Reflux;	A n/a B 91%

tetraphenyldiphosphine oxide (2096-83-5) + Cp2Ti=CH2 → bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
Stage #1: tetraphenyldiphosphine oxide; Cp2Ti=CH2 In benzene at 50℃; Stage #2: at 80℃;	66%

dichloromethane (75-09-2) + diphenylphosphane (829-85-6) → bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
With tris(dimethylamino)(methylimino)phosphorane In tetrahydrofuran; diethyl ether for 24h; Ambient temperature;	50%
With potassium hydroxide; potassium carbonate 1.) HMPT, 20 deg C, 2.) 40 - 45 deg C, 1 h; Yield given. Multistep reaction;
With potassium hydroxide; potassium carbonate 1) HMPA, 20 deg C, 2) HMPA, 40-45 deg C, 1 h; Yield given. Multistep reaction;

chloroform (67-66-3) + potassium diphenylphosphine (15475-27-1, 4346-39-8) → Tetraphenyldiphosphin (1101-41-3) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
In ammonia at -50℃;	A n/a B 45%
In ammonia at -50℃; Product distribution; Mechanism; another solvent;	A n/a B 45%

chloro-diphenylphosphine (1079-66-9) → bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
With sodium und Umsetzung mit CH2Cl2;

(diphenylphosphinomethyl)diphenylphosphine sulphide (54006-28-9) → bis(diphenylthiophosphoryl)methane (14633-92-2) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
at 150℃; vacuum;
at 150℃; vacuum sublimation;

Lithium-bis(diphenylphosphanyl)methanid (28926-61-6) + <18>Krone-6-Kaliumdicyanphosphid → C26H21NP3(1-)*C12H24O6*K(1+) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
In tetrahydrofuran for 0.25h; Ambient temperature;

C25H21CsP2 (80359-57-5) + cyclohexylamine (108-91-8) → Caesium-cyclohexylamid (4820-05-7) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
Equilibrium constant; pK;

1,2-dichloro-ethane (107-06-2) → ethene (74-85-1) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
With Pd2(bis(diphenylphosphino)methane)3 Quantum yield; Irradiation;

chlorobromomethane (74-97-5) + diphenylphosphane (829-85-6) → bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
With phosphazene base-P4-tert-butyl In tetrahydrofuran; diethyl ether for 24h; Ambient temperature; Yield given;

dichloromethane (75-09-2) + triphenylphosphine (603-35-0) → bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
With lithium In tetrahydrofuran at 0℃; for 0.5h;

PdPtCoI(CO)3(dppm)2 (113132-12-0) → {Pd(η2-dppm)(DMSO)2}I2 (113132-19-7) + {Pt(η2-dppm)(DMSO)2}I2 (113132-15-3) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
With iodine In dimethyl sulfoxide To a soln. of PdPtCoI(CO)3(dppm)2 in DMSO was added I2. This resulted in an immediate color change from deep red to red-orange.; Not isolated. Detected by (31)P-NMR.;

CO2(CO)2(μ-CO){bis(diphenylphosphino)methane}2 → Co2(CO)4(μ-CO)2(μ-bis(diphenylphosphino)methane) (52615-19-7) + {Co(CO)3(((C6H5)2P)2CH2)}(1+)*{Co(CO)4}(1-)={Co(CO)3(((C6H5)2P)2CH2)}{Co(CO)4} + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
With CO In not given in presence of CO; not isolated; detected by NMR;

cis-bis(pentafluorophenyl)bis(bis(diphenylphosphino)methane)palladium → Pd(C6F5)2(dppm) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
In not given equilibrium in soln.; (31)P NMR data;

Pt((C6H5)2PCH2P(C6H5)2)2(C6F5)2 (114248-14-5, 84663-41-2) → bis(diphenylphosphino)methane(P,P')bis(pentafluorophenyl)platinum(II) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
In not given equilibrium in soln.; (31)P NMR data;

Pd2(bis(diphenylphosphino)methane)3 → (μ2-CH2)(Cl)2(bis(diphenylphosphino)methane)2dipalladium (78274-94-9) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
With dichloromethane In dichloromethane Irradiation (UV/VIS);

[Pd(mesityl)(bis(diphenylphosphino)methane-PP)(bis(diphenylphosphino)methane-P)](1+) → [Pd2(mesityl)2(μ-Cl)(μ-dppm)2](1+) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
In dichloromethane warming the soln. to ambient temp.;

{Co2(CO)2(μ-CO)(μ-I)(μ-dppm)2}I → bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: Zn / acetonitrile 2: CO / not given View Scheme

Co2(CO)4(μ-CO)2(μ-bis(diphenylphosphino)methane) (52615-19-7) → {Co(CO)3(((C6H5)2P)2CH2)}(1+)*{Co(CO)4}(1-)={Co(CO)3(((C6H5)2P)2CH2)}{Co(CO)4} + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: I2 / tetrahydrofuran 2: Zn / acetonitrile 3: CO / not given View Scheme

trans-bis(pentafluorophenyl)bis(bis(diphenylphosphino)methane)palladium → Pd(C6F5)2(dppm) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: not given 2: not given View Scheme

diphenyl(trimethylsilylmethyl)phosphane (4451-96-1) → bis[{(trimethylsilyl)methyl}phenylphosphino]methane (1159248-32-4) + <(Diphenylarsino)methyl>diphenylphosphan (69783-37-5) + C14H14As2Cl3P + C39H36AsP3 + Diphenylphosphine oxide (4559-70-0) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
With arsenic trichloride In neat (no solvent) at 90 - 100℃; Solvent;

dichlorophenylarsine (696-28-6) + diphenyl(trimethylsilylmethyl)phosphane (4451-96-1) → dpma (97551-44-5) + <(Diphenylarsino)methyl>diphenylphosphan (69783-37-5) + bis(diphenylphosphino)methane monooxide (23176-18-3) + dpap + diphenyl(methyl)phosphine (1486-28-8) + bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
In neat (no solvent) at 90 - 100℃; Inert atmosphere;

mer,cis-(Mn(CO)2(dppm-PP')(dppm-P)Br) (84277-68-9, 84232-89-3, 224444-98-8, 224444-99-9) → bis-diphenylphosphinomethane (2071-20-7)

Conditions	Yield
With sodium methylate In methanol for 72h; Guerbet Reaction; Glovebox;

bis-diphenylphosphinomethane (2071-20-7) → bis(diphenylphosphoryl)methane (2071-21-8)

Conditions	Yield
With HOF* CH3CN In dichloromethane at 0℃; for 0.0833333h;	100%
With dihydrogen peroxide In dichloromethane; water for 0.0833333h;	93%
With dihydrogen peroxide In tetrahydrofuran; water at 20℃; for 2h;	90%

{(carbonyl)3cobalt(μ-hexafluorobut-2-yne)cobalt(carbonyl)3} (37685-63-5) + bis-diphenylphosphinomethane (2071-20-7) → (CF3)2C2*Co2*4CO*(C6H5)2PCH2P(C6H5)2 = (CF3)2C2Co2(CO)4((C6H5)2PCH2P(C6H5)2)

Conditions	Yield
With benzophenone ketyl In not given inert gas; 293 K; a small amount benzophenone ketyl was added to a solution of the metal complex and the P-compound; solvent was removed; chromatographed;	100%

(bicyclo[2.2.1]hepta-2,5-diene)tetracarbonylmolybdenum(0) (12146-37-1, 124717-04-0) + bis-diphenylphosphinomethane (2071-20-7) → tetracarbonyl-bis(diphenylphosphino)methane-molybdenum(0) (26743-81-7) + bicyclo[2.2.1]hepta-2,5-diene (121-46-0)

Conditions	Yield
In tetrahydrofuran reaction in a calorimeter under argon;	A 100% B n/a

dichlorotetrakis(dimethylsulfoxide)ruthenium(II) + bis-diphenylphosphinomethane (2071-20-7) → cis-dichlorodi[bis(diphenylphosphino)methane]ruthenium(II)

Conditions	Yield
In toluene (N2 or Ar); complex added to ligand soln., suspn. stirred at 80°C for 15 h; filtered off, washed with toluene and Et2O;	100%
In toluene at 80℃; for 12h;

trichlorotris(tetrahydrofuran)molybdenum(III) (31355-55-2, 39210-30-5) + bis-diphenylphosphinomethane (2071-20-7) → trichloro(1,2-diphenylphosphinomethane)dimolybdenum(III)

Conditions	Yield
Mo(III) complex and excess diphosphine heating to melting point of the diphosphine for 10 min, on cooling the solid washing with hot toluene; identified by elem. anal., and IR spectrum;	100%

bis-diphenylphosphinomethane (2071-20-7) + platinum(II) chloride → (Pt((C6H5)2PCH2P(C6H5)2)2)2(1+)*Cl(1-)=[Pt((C6H5)2PCH2P(C6H5)2)2]2Cl

Conditions	Yield
In acetone PtCl2 was reacted with ligand in boiling acetone for 5 h;	100%

pentacarbonyl-(μ-di-tert-butylphosphido)-(μ-dicyclohexylphosphido)diiron (140657-01-8) + bis-diphenylphosphinomethane (2071-20-7) → [Fe2(CO)5(P(C(CH3)3)2)(P((CH(CH2)5))2)((C6H5)2PCH2P(C6H5)2)]*0.5C4H8O

Conditions	Yield
In tetrahydrofuran (Ar); stirring (25°C, 2 h); solvent removal (vac.), extracting (pentane), filtn., solvent redn. (vac.), crystn. (-30°C); elem. anal.;	100%

dichloromethane (75-09-2) + silver(I) 3,5-difluorophenylthiolate + bis-diphenylphosphinomethane (2071-20-7) → C13H8F4S2 + C75H66Ag3Cl2P6(1+)*C6HF4S(1-)*Ag(1+)*Cl(1-)

Conditions	Yield
for 0.0833333h; Sonication;	A 100% B n/a

trichlorotris(tetrahydrofuran)chromium(III) (10170-68-0, 16997-54-9) + bis-diphenylphosphinomethane (2071-20-7) → [(bis(diphenylphosphino)methane)CrCl2(μ-Cl)]2

Conditions	Yield
In not given ligand reacted with Cr complex (A.Bollmann, K.Blann, J.T.Dixon, F.M.Hess, E.Killian et al. J. Am. Chem. Soc. 126 (2004) 14712); elem. anal.;	99%

[(PPh3)ClPd(μ-[C=C(H)-N=CPh2])PdCl(PPh3)2]*toluene (537690-23-6) + bis-diphenylphosphinomethane (2071-20-7) → [ClPd(μ-dppm)2(μ-[C=C(H)-N=CPh2])PdCl]

Conditions	Yield
In dichloromethane byproducts: PPh3; all manipulations under purified N2; org. compd. added to soln. of Pd complex, stirred for 10 min; solvent removed in vac., residue rinsed with Et2O, dried, elem. anal.;	99%

[MoCl(SnCl3)(CO)3(NCCH3)2] (120254-22-0) + bis-diphenylphosphinomethane (2071-20-7) → MoCl(SnCl3)(CO)3((C6H5)2P(CH2)P(C6H5)2) (120190-02-5)

Conditions	Yield
In acetone stirring 30 min, under dry nitrogen stream; removal of solvent in vacuo, elem anal.;	99%

cis-dirhenium diacetate tetrachloride dihydrate (14705-94-3, 29131-21-3) + bis-diphenylphosphinomethane (2071-20-7) → [Re2Cl4(μ-bis(diphenylphosphino)methane)2] (58298-10-5)

Conditions	Yield
In ethanol by refluxing ethanol soln. contg. cis-Re2(μ-O2CCH3)2Cl4(H2O)2 and bis(diphenylphosphino)methane for 18 h under N2;	99%

ammonium hexafluorophosphate + phenylchloro(1,5-cyclooctadiene)platinum(II) + bis-diphenylphosphinomethane (2071-20-7) → Pt2Cl(CH2(P(C6H5)2)2)2(C6H5)2(1+)*PF6(1-)=(Pt2Cl(CH2(P(C6H5)2)2)2(C6H5)2)PF6

Conditions	Yield
In dichloromethane byproducts: cyclooctadiene; under Ar; to a soln. of the Pt complex and the phosphine in CH2Cl2 was added NH4PF6, stirred for 3 h; solvent was removed, washed with pentane, redissolved in CH2Cl2, passed through an alumina column, evapd. to dryness, washed with pentane, dried in vac.; elem. anal.;	99%

[Mo2(η5-cyclopentadienyl)2(μ-H)(μ-PCy2)(CO)2] (537683-54-8) + bis-diphenylphosphinomethane (2071-20-7) → [Mo2(η5-cyclopentadienyl)2(μ-H)(μ-PCy2)(CO)2(μ-bis(diphenylphosphino)methane)]

Conditions	Yield
In toluene (N2); stirring molybdenum compd. and phosphine deriv. in toluene at roomtemp. for 2 h;	99%

1,4-pyrazine (290-37-9) + methanol (67-56-1) + bis-diphenylphosphinomethane (2071-20-7) + copper(I) bromide (7787-70-4) → ([Cu3(bis(diphenylphosphino)methane)3Br2][Cu2(bis(diphenylphosphino)methane)(pyrazine)Br2]Br(CH3OH)2)n

Conditions	Yield
In dichloromethane mixt. of CuBr, C4H4N2 and (Ph2P)2CH2 (1:2:1 molar ratio) in CH2Cl2 stirred (6 h, ambient temp.); elem. anal.;	99%

Co2(CO)6CC((thiophene-2,5-diyl)Fe(η5-C5H5)(dppe))2 + bis-diphenylphosphinomethane (2071-20-7) → Co2(CO)4(dppm)CC((thiophene-2,5-diyl)Fe(η5-C5H5)(dppe))2

Conditions	Yield
heating;	99%

Co2(CO)6CC((thiophene-2,5-diyl)Fe(η5-C5H4Me)(dppe))2 + bis-diphenylphosphinomethane (2071-20-7) → Co2(CO)4(dppm)CC((thiophene-2,5-diyl)Fe(η5-C5H4Me)(dppe))2

Conditions	Yield
heating;	99%

silver trifluoromethanesulfonate (2923-28-6) + mercuric triflate (49539-99-3, 49540-00-3) + mercury + bis-diphenylphosphinomethane (2071-20-7) → AgHg2[(C6H5)2PCH2P(C6H5)2]3(3+)*3CF3SO3(1-)=AgHg2[(C6H5)2PCH2P(C6H5)2]3(O3SCF3)3

Conditions	Yield
In dichloromethane	99%

silver nitrate + propargyl alcohol (107-19-7) + bis-diphenylphosphinomethane (2071-20-7) → [Ag3(μ3-η(1)-CCCH2OH)(μ-diphenylphosphinomethane)3](NO3)2

Conditions	Yield
With Et3N In acetonitrile byproducts: [Et3NH]NO3; alcohol-comp. then excess of Et3N were added to 3 equiv. of AgNO3 in MeCN, stirring for 3 h, 3 equiv. of solid P-compd. was added, stirring for 18 h; soln. was filtered through Celite, evapd. to dryness, solid was washed with H2O, Et2O and dried, recrystn. from CH2Cl2/hexane;	99%

2,4,6-trimethylbenzylbromide (4761-00-6) + bis-diphenylphosphinomethane (2071-20-7) → [(diphenylphosphino)methyl]diphenyl[(2,4,6-trimethylphenyl)methyl]phosphonium bromide (1372787-36-4)

Conditions	Yield
In toluene at 80℃; for 48h; Inert atmosphere;	99%

N,N,N-(ferrocenylmethyl)trimethylammonium iodide + bis-diphenylphosphinomethane (2071-20-7) → (diphenylphosphinomethyl)(ferrocenylmethyl)diphenylphosphoniumiodide (84469-70-5)

Conditions	Yield
In N,N-dimethyl-formamide byproducts: N(CH3)3; (N2), mixture stirred for 5 hat 120°C, cooled to 20°C; solvent removed in vacuo, residue washed with toluene and pentane, dried in vacuo;	98.5%

p-methylazidobenzene (2101-86-2) + bis-diphenylphosphinomethane (2071-20-7) → bis(N-p-tolyliminodiphenylphosphoranyl)methane (33535-76-1)

Conditions	Yield
In benzene at 60℃; for 4h;	98%

bis-diphenylphosphinomethane (2071-20-7) → C25H22Br2P2(2+)*2Br(1-)

Conditions	Yield
With bromine In dichloromethane	98%
With bromine In dichloromethane at -78 - 20℃;	100 % Spectr.

dodecacarbonyl-triangulo-triruthenium (15243-33-1) + bis-diphenylphosphinomethane (2071-20-7) → (Ru3(CO)11)2((C6H5)2PCH2P(C6H5)2) (86277-00-1)

Conditions	Yield
With sodium diphenylketyl In tetrahydrofuran a THF soln. of Ph2CONa was added dropwise under N2 to a soln. of Ru3(CO)12 and dppm in 2:1 molar ratio in THF, reaction was monitored by IR spectroscopy; THF was pumped off under vac., residue recrystd.; elem. anal.;	98%

[2,2]bipyridinyl (366-18-7) + silver perchlorate + bis-diphenylphosphinomethane (2071-20-7) → [Ag2(2,2'-bipyridyl)2(dppm)][ClO4]2

Conditions	Yield
In acetonitrile stoich. mixt. in CH3CN stirred for 12 h at room temp.; evapd., washed (Et2O), elem. anal.;	98%

potassium tetrachloroplatinate(II) (10025-99-7) + bis-diphenylphosphinomethane (2071-20-7) → Pt2(bis(diphenylphosphino)methane)3

Conditions	Yield
With NaBH4 In acetonitrile (N2); stirring (12 h); filtn., washing (pentane), drying;	98%

Co4(CO)9{HC(PPh2)3} + bis-diphenylphosphinomethane (2071-20-7) → Co4(CO)7(H2C(P(C6H5)2)2)(HC(P(C6H5)2)3) (93279-94-8)

Conditions	Yield
In tetrahydrofuran refluxed in THF for 2 h; filtered through silica gel, evapd. to dryness; washed with diethylether;	98%

silver(I) hexafluorophosphate (26042-63-7) + (Rh2(CNC(CH3)3)4((C6H5)2PCH2P(C6H5)2)2)(2+)*2PF6(1-)=(Rh2(CNC(CH3)3)4((C6H5)2PCH2P(C6H5)2)2)(PF6)2 + bis-diphenylphosphinomethane (2071-20-7) → (((CH3)3CNC)2Rh((C6H5)2PCH2P(C6H5)2)2Ag)(2+)*2PF6(1-)*0.5C6H14=(((CH3)3CNC)2Rh((C6H5)2PCH2P(C6H5)2)2Ag)(PF6)2*0.5C6H14

Conditions	Yield
With n-hexane In dichloromethane; acetone ligand was added to soln. of Rh-complewx in dichloromethane, followed by soln. of AgPF6 in acetone, soln. stirred for 5 min; Et2O added, soln. filtered, filtrate evapd. to dryness under reduced pressure, residue triturated with Et2O, filtered off, washed with Et2O anddried in vacuo over P2O5, product recrystd. from acetone-n-hexane; elem. anal.;	98%

carbonylchlorohydridotris(triphenylphosphine)ruthenium(II) (157072-60-1, 166941-05-5, 16971-33-8, 61521-25-3) + bis-diphenylphosphinomethane (2071-20-7) → [RuHCl(CO)(PPh3)2(dppm)] (157931-40-3, 157969-03-4)

Conditions	Yield
In toluene in an oxygen-free environment; a suspn. of the Ru complex in toluene was treated with the phosphine, refluxed for 30 min; cooled to room temp., concd. in vac., slow addn. of pentane, filtered, washed with pentane and Et2O, dried in vac. (mixt. of cis- and trans-isomers); elem. anal.;	98%
In dichloromethane under N2 or Ar; addn. of phosphine to a CH2Cl2 soln. of the Ru complex,mixt. stirred (23°C, 72 h); mixt. cooled (-15°C), crystals filtered off, washed (Et2O); the mixt. of isomers could not be sepd.;	70%

Upstream product

• 1079-66-9 chloro-diphenylphosphine 
• 67-66-3 chloroform 
• 15475-27-1 potassium diphenylphosphine 
• 54006-28-9 (diphenylphosphinomethyl)diphenylphosphine sulphide 
• 28926-61-6 Lithium-bis(diphenylphosphanyl)methanid 
• 80359-57-5 C₂₅H₂₁CsP₂ 
• 108-91-8 cyclohexylamine 
• 107-06-2 1,2-dichloro-ethane 
• 75-09-2 dichloromethane 
• 829-85-6 diphenylphosphane 
• 74-97-5 chlorobromomethane 
• 603-35-0 triphenylphosphine 
• 2096-83-5 tetraphenyldiphosphine oxide 
• 74-95-3 1,1-dibromomethane 

Downstream Products

• 28926-65-0 Tris(diphenylphosphino)methan 
• 72337-97-4 C₃₇H₃₁P₃ 
• 74144-32-4 1,1,3,3-Tetraphenyl-1,3-diphosphoniacyclohexan-dibromid 
• 66479-01-4 5-hydroxy-1,1,3,3-tetraphenyl-[1,3]diphosphinanediium; dibromide 
• 35497-19-9 5-oxo-1,1,3,3-tetraphenyl-[1,3]diphosphinanediium; dibromide 
• 40057-80-5 5-oxo-1,1,3,3-tetraphenyl-[1,3]diphosphinanediium; dibromide 
• 70575-31-4 C₃₃H₃₉P₃ 
• 38452-92-5 1,1,3,3,5,5-Hexaphenyl-2,4-diaza-1,3,5-triphosphabenzene 
• 38452-94-7 6-methyl-2,2,4,4-tetraphenyl-2λ⁵,4λ⁵-[1,5,2,4]diazadiphosphinine 
• 38452-99-2 6-methyl-2,2,4,4-tetraphenyl-2,3-dihydro-4λ⁵-[1,5,2,4]diazadiphosphininium; chloride 
• 38452-97-0 2,2,4,4,6-pentaphenyl-2λ⁵,4λ⁵-[1,5,2,4]diazadiphosphinine 
• 38453-00-8 2,2,4,4-tetraphenyl-2λ⁵,4λ⁵-[1,5,2,4]diazadiphosphinine 
• 38452-95-8 6-ethyl-2,2,4,4-tetraphenyl-2λ⁵,4λ⁵-[1,5,2,4]diazadiphosphinine 
• 38452-96-9 6-benzyl-2,2,4,4-tetraphenyl-2λ⁵,4λ⁵-[1,5,2,4]diazadiphosphinine 

Relevant articles and documents

1,2-addition of diphosphine monoxide to a double bond of a titanocene carbene complex

A titanocene carbene complex reacted with diphosphine monoxide to give R2PCH2PR2.

Manganese Diphosphine and Phosphinoamine Complexes Are Effective Catalysts for the Production of Biofuel Alcohols via the Guerbet Reaction

We report a variety of manganese-based catalysts containing both chelating diphosphine (bis(diphenylphosphino)methane (dppm: 1, 2, and 7) or 1,2-bis(diphenylphosphino)ethane (dppe: 3)), and mixed-donor phosphinoamine (2-(diphenylphosphino)ethylamine (dppea: 4-6)) ligands for the upgrading of ethanol and methanol to the advanced biofuel isobutanol. These catalysts show moderate selectivity up to 74% along with turnover numbers greater than 100 over 90 h, with catalyst 2 supported by dppm demonstrating superior performance. The positive effect of substituting the ligand backbone was also displayed with a catalyst supported by C-phenyl-substituted dppm (8) having markedly improved performance compared to the parent dppm catalysts. Catalysts supported by the phosphinoamine ligand dppea are also active for the upgrading of ethanol to n-butanol. These results show that so-called PNP-pincer ligands are not a prerequisite for the use of manganese catalysts in Guerbet chemistry and that simple chelates can be used effectively.

Photoreactions of Palladium Phosphine Complex with Chloroalkane. Production of Ethylene with 1,2-Dichloroethane and Novel Photochromic Behavior

Photoirradiation on 02(dppm)3> (dppm = bis(diphenylphosphino)methane) in 1,2-dichloroethane solution with visible light yields I2Cl2(dppm)2> (2) and ethylene quantitatively.Irradiation of 2 in various solutions shows interesting photochromic behavior.

Rearrangement and redistribution reaction of Ph2PCH2TMS with PhAsCl2 or AsCl3

The attempted synthesis of bis(diphenylphosphinomethyl) phenylarsane and tris(diphenylphosphinomethyl) arsane through condensation of chloro arsanes and diphenyl (trimethylsilylmethyl) phosphane yielded a number of side products originating from migratory and redox-reactions in addition to the targeted ligands. An unexpected, 1,3,4-phosphadiarssolan-1-ium salt was obtained and crystallographically characterized as an A-shaped chlorido adduct.

Ethylene oligomerization catalyst systems having enhanced selectivity

Disclosed herein is a catalyst system for selective oligomerization of ethylene, which comprises a P—C—C—P frame-work ligand, which is (R1)(R2)P—(R5)CHCH(R6)—P(R3)(R4), and a chromium-based metal compound. Also disclosed is a method of greatly enhancing the activity and selectivity of oligomerization, such as trimerization or tetramerization, using a ligand having a specific steric arrangement structure.

ETHYLENE TETRAMERIZATION CATALYST SYSTEMS AND METHOD FOR PREPARING 1-OCTENE USING THE SAME

Disclosed herein is a method of preparing 1-octene at high activity and high selectivity while stably maintaining reaction activity by tetramerizing ethylene using a chromium-based catalyst system comprising a transition metal or a transition metal precursor, a cocatalyst, and a P—C—C—P backbone structure ligand represented by (R1)(R2)P—(R5)CHCH(R6)—P(R3)(R4).

Catalyst-free alcoholysis of phosphane-boranes: a smooth, cheap, and efficient deprotection procedure

Catalyst-free alcoholytic deprotection of borane-protected phosphorus compounds offers a smooth, efficient, and clean alternative to existing deprotection methods. In this paper we report our results on the general applicability of deprotecting phosphane-

A mild and efficient CsOH-promoted synthesis of ditertiary phosphines

A mild and efficient method for the synthesis of ditertiary phosphines has been developed. In the presence of cesium hydroxide, molecular sieves, and DMF, various dihalides were coupled with diphenylphosphine at room temperature, and the results have demonstrated that this methodology offers a general synthetic procedure producing a variety of ditertiary phosphines in high yields.

CsOH-promoted P-alkylation: A convenient and highly efficient synthesis of tertiary phosphines

A mild and efficient method for the synthesis of tertiary phosphines and ditertiary phosphines has been developed. In the presence of cesium hydroxide, molecular sieves and DMF at room temperature, various secondary phosphines and alkyl bromides were examined, and the results have demonstrated that this methodology offers a general synthetic procedure to produce tertiary phosphines in moderate to high yields. Optically active tertiary phosphine synthesis is also described.

General route to halide-bridged organopalladium A-frame complexes and studies of reductive elimination from these bimetallic systems

Reactions of [Pd2Cl2(μ-dppm)2] with RMgX (R = Me, Et, Bu, Ph, C6H4Me-4) at low temperature, followed by addition of CBr4 and excess NH4PF6 or 1 equiv of TIPF6, provided halide-bridged organopalladium A-frame complexes of the form [Pd2R2(μ-X)(μ-dppm)2]PF6. Mixed metal complexes were obtained similarly starting from [PdCtCl2(μ-dppm)2]. Unsymmetrical A-frames of the type [Pd2(C6H2Me3-2,4,6)R(μ-Cl)(μ-d ppm)2]+ were generated reaction of [Pd(C6H2Me3-2,4,6) (dppm)2]+ (obtained by treatment of [PdCl2 (cod)] w mesitylmagnesium bromide at low temperature, followed by 2 equiv of dppm) with [Pd2R2(μ-Cl)2 (AsPh3)2]. The organopalladium A-frames did not react readily with CO, but the corresponding acyl derivatives [Pd2(COR)2(μ-Cl)(μ-dppm)2]PF6 were produced by carbonylation of [Pd2R2(μ-Cl)2(AsPh3)2] followed by addition of dppm (R = Me, Et, Bn). Thermal decomposition of [Pd2(CH2Ph)2(μ-Cl)(μ-dppm)2]Cl was found to be first order in A-frame and resulted in quantitative formation of [Pd2Cl2(μ-dppm)2] and 1,2-diphenylethane. The methyl and aryl complexes underwent both reductive elimination and hydrogen abstraction reactions. [Pd2Et2(μ-Br)(μ-ddpm)2]PF6 decomposed by β-hydride elimination and subsequent reductive elimination to yield ethene and ethane, whereas the butyl derivative gave both 1- and 2-butene. Acetic acid was formed when [Pd2(COMe)2(μ-Cl)(μ-dppm)2]PF6 was heated in dmso-d6 solution, but decarbonylation was the predominant process in dioxane. The molecular structures of [Pd2(CH2Ph)2(μ-Br)(μ-dppm)2] PF6·H2O, 2C6H6 and [Pd2Cl2(μ-Cl)(μ-dppm)2]OH· 0.5(CH3)2CO are also described.