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{{Chembox |
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{{Chembox |
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| verifiedrevid = 396340478 |
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|verifiedrevid = 440893139 |
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| Name = '''Dichlorotris(triphenylphosphine)ruthenium(II)''' |
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|Name = Dichlorotris(triphenylphosphine){{SHY}}ruthenium(II) |
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|ImageFile1 = RuCl2P3Ibers.png |
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| ImageFile2 = Dichlorotris(triphenylphosphine)ruthenium(II).png |
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|ImageSize1 = 180px |
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| ImageSize2 = 240px |
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| ImageName = Dichlorotris(triphenylphosphine)ruthenium(II) |
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|ImageName1 = Dichlorotris(triphenylphosphine)ruthenium(II) |
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| IUPACName = Dichlorotris(triphenylphosphine)ruthenium(II) |
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|ImageFile2 = Dichlorotris(triphenylphosphine)ruthenium(II)-from-xtal-3D-bs-17.png |
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| OtherNames = Ruthenium tris(triphenylphosphine) dichloride; Tris(triphenylphosphine)dichlororuthenium; Tris(triphenylphosphine)ruthenium dichloride;Tris(triphenylphosphine)ruthenium(II) dichloride |
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|IUPACName = Dichlorotris(triphenylphosphine)ruthenium(II) |
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|OtherNames = Ruthenium tris(triphenylphosphine) dichloride; Tris(triphenylphosphine)dichlororuthenium; Tris(triphenylphosphine)ruthenium dichloride;Tris(triphenylphosphine)ruthenium(II) dichloride |
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| Section1 = {{Chembox Identifiers |
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|Section1 = {{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 76650 |
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|ChemSpiderID = 76650 |
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|PubChem = 11007548 |
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| InChI = 1/3C18H15P.2ClH.Ru/c3*1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;;;/h3*1-15H;2*1H;/q;;;;;+2/p-2 |
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|InChI = 1/3C18H15P.2ClH.Ru/c3*1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;;;/h3*1-15H;2*1H;/q;;;;;+2/p-2 |
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| SMILES = ...c3c(P(c1ccccc1)c2ccccc2)cccc3.c1ccccc1P(c2ccccc2)c3ccccc3.c1ccccc1P(c2ccccc2)c3ccccc3 |
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|SMILES = ...c3c(P(c1ccccc1)c2ccccc2)cccc3.c1ccccc1P(c2ccccc2)c3ccccc3.c1ccccc1P(c2ccccc2)c3ccccc3 |
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| InChIKey = WIWBLJMBLGWSIN-NUQVWONBAX |
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|InChIKey = WIWBLJMBLGWSIN-NUQVWONBAX |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI = 1S/3C18H15P.2ClH.Ru/c3*1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;;;/h3*1-15H;2*1H;/q;;;;;+2/p-2 |
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|StdInChI = 1S/3C18H15P.2ClH.Ru/c3*1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;;;/h3*1-15H;2*1H;/q;;;;;+2/p-2 |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = WIWBLJMBLGWSIN-UHFFFAOYSA-L |
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|StdInChIKey = WIWBLJMBLGWSIN-UHFFFAOYSA-L |
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| CASNo = 15529-49-4 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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|CASNo = 15529-49-4 |
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|CASNo_Ref = {{cascite|correct|CAS}} |
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| EINECS = 239-569-7 |
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|EINECS = 239-569-7 |
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}} |
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| Section2 = {{Chembox Properties |
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|Section2 = {{Chembox Properties |
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| Formula = C<sub>54</sub>H<sub>45</sub>Cl<sub>2</sub>P<sub>3</sub>Ru |
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|Formula = C<sub>54</sub>H<sub>45</sub>Cl<sub>2</sub>P<sub>3</sub>Ru |
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| MolarMass = 958.83 g/mol |
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|MolarMass = 958.83 g/mol |
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| Appearance = Black Crystals or Red-Brown |
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|Appearance = Black Crystals or Red-Brown |
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| Density = 1.43 g/cm<sub>3</sub> |
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|Density = 1.43 g cm<sup>−3</sup> |
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| MeltingPtK = 406 |
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|MeltingPtK = 406 |
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| Air Sensitive |
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| Section3 = {{Chembox Structure |
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|Section3 = {{Chembox Structure |
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| Crystal Structure = Monoclinic |
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|CrystalStruct = Monoclinic |
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|LattConst_a = 18.01 Å |
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| Crystal Parameters = a = 18.01 Å, b = 20.22 Å, c = 12.36 Å, β = 90.5<sup>o</sup> |
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|LattConst_b = 20.22 Å |
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| Space Group = C<sub>2h</sub><sup>5</sup>-P2<sub>1/c</sub> |
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|LattConst_c = 12.36 Å |
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| Coordination Geometry = Octahedral |
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|LattConst_beta = 90.5 |
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|SpaceGroup = C<sub>2h</sub><sup>5</sup>-P2<sub>1/c</sub> |
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|Coordination = Octahedral |
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}} |
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|Section4 ={{Chembox Hazards |
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|GHSPictograms = {{GHS07}} |
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|GHSSignalWord = Warning |
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|HPhrases = {{H-phrases|302|312|332}} |
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|PPhrases = {{P-phrases|261|264|270|271|280|301+312|302+352|304+312|304+340|312|322|330|363|501}} |
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'''Dichlorotris(triphenylphosphine)ruthenium(II)''' is a ] of ]. This chocolate brown solid is a precursor to other complexes including those used as ]. |
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'''Dichlorotris(triphenylphosphine)ruthenium(II)''' is a ] of ]. It is a chocolate brown solid that is soluble in organic solvents such as ]. The compound is used as a precursor to other complexes including those used in ]. |
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==Synthesis and basic properties== |
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==Synthesis and basic properties== |
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RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> is the product of the reaction of ] trihydrate with a methanolic solution of ].<ref>Stephenson, T. A.; Wilkinson, G. “New Complexes of Ruthenium (II) and (III) with Triphenylphosphine, Triphenylarsine, Trichlorostannate, Pyridine, and other Ligands”, ''J. Inorg. Nucl. Chem.'', '''1966''', ''28'', 945-956. {{DOI|10.1016/0022-1902(66)80191-4}}</ref><ref>P. S. Hallman, T. A. Stephenson, G. Wilkinson "Tetrakis(Triphenylphosphine)Dichloro-Ruthenium(II) and Tris(Triphenylphosphine)-Dichlororuthenium(II)" Inorganic Syntheses, 1970 Volume 12, . {{DOI|0.1002/9780470132432.ch40}}</ref> |
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RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> is the product of the reaction of ] trihydrate with a ]ic solution of ].<ref>Stephenson, T. A.; Wilkinson, G. "New Complexes of Ruthenium (II) and (III) with Triphenylphosphine, Triphenylarsine, Trichlorostannate, Pyridine, and other Ligands", ''J. Inorg. Nucl. Chem.'', '''1966''', ''28'', 945-956. {{doi|10.1016/0022-1902(66)80191-4}}</ref><ref>P. S. Hallman, T. A. Stephenson, G. Wilkinson "Tetrakis(Triphenylphosphine)Dichloro-Ruthenium(II) and Tris(Triphenylphosphine)-Dichlororuthenium(II)" ''Inorganic Syntheses'', 1970 volume 12 {{doi|10.1002/9780470132432.ch40}}</ref> |
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:2 RuCl<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub> + 7 PPh<sub>3</sub> → 2 RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> + 2 HCl + 5 H<sub>2</sub>O + 1 OPPh<sub>3</sub> |
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:2 RuCl<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub> + 7 PPh<sub>3</sub> → 2 RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> + 2 HCl + 5 H<sub>2</sub>O + OPPh<sub>3</sub> |
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When conducted in the presence of larger excess of triphenylphosphine, the synthesis affords black RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>4</sub>. |
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The coordination sphere of RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> can be viewed as either five-coordinate or octahedral. One coordination site is occupied by one of the hydrogen atoms of a phenyl group.<ref>Sabo-Etienne, S.; Gellier, M., “Ruthenium: Inorganic and Coordination Chemistry”, ''Encyclopedia of Inorganic Chemistry'', '''2006''', John Wiley & Sons. {{DOI|10.1002/0470862106.ia208}}</ref> This Ru---H ] is long (2.59 Å) and weak. The low symmetry of the compound is reflected by the differing lengths of the Ru-P bonds: 2.374, 2.412, and 2.230 Å.<ref>La Placa, S. J.; Ibers, J.A., “A Five-Coordinated d<sup>6</sup> Complex: Structure of Dichlorotris(triphenylphosphine)ruthenium(II)”, ''Inorganic Chemistry'', '''1965''', 4, 778-78. {{DOI|10.1021/ic50028a002}}</ref> The Ru-Cl bond lengths are both 2.387 Å. |
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The coordination sphere of RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> can be viewed as either five-coordinate or octahedral. One coordination site is occupied by one of the hydrogen atoms of a phenyl group.<ref>{{cite book|doi=10.1002/0470862106.ia208|chapter=Ruthenium: Inorganic & Coordination Chemistry ''Based'' in part on the article Ruthenium: Inorganic & Coordination Chemistry by Bruno Chaudret & Sylviane Sabo-Etienne which appeared in the ''Encyclopedia'' of Inorganic Chemistry, First Edition|title=Encyclopedia of Inorganic Chemistry|year=2006|last1=Sabo-Etienne|first1=Sylviane|last2=Grellier|first2=Mary|isbn=0470860782}}</ref> This Ru---H ] is long (2.59 Å) and weak. The low symmetry of the compound is reflected by the differing lengths of the Ru-P bonds: 2.374, 2.412, and 2.230 Å.<ref>{{cite journal|doi = 10.1021/ic50028a002|title = A Five-Coordinated d6 Complex: Structure of Dichlorotris(triphenylphosphine)ruthenium (II)|year = 1965|last1 = La Placa|first1 = Sam J.|last2 = Ibers|first2 = James A.|journal = Inorganic Chemistry|volume = 4|issue = 6|pages = 778–783}}</ref> The Ru-Cl bond lengths are both 2.387 Å. |
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==Reactions== |
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==Substitution reactions== |
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In the presence of excess of triphenylphosphine, RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> binds a fourth phosphine to give black RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>4</sub>. The triphenylphosphine ligands in both the tris(phosphine) and tetrakis(phosphine) complexes are readily substituted by other ligands. The tetrakis(phosphine) complex is a precursor to the ]s.<ref>{{cite journal|doi=10.1021/cr9002424|title=Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts|year=2010|last1=Vougioukalakis|first1=Georgios C.|last2=Grubbs|first2=Robert H.|journal=Chemical Reviews|volume=110|issue=3|pages=1746–1787|pmid=20000700}}</ref> |
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The triphenylphosphine ligands are labile and are readily substituted by other ligands. Dichlorotris(triphenylphosphine)ruthenium(II) reacts with ] to produce the all trans isomer of dichloro(dicarbonyl)bis(triphenylphosphine)ruthenium(II). |
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Dichlorotris(triphenylphosphine)ruthenium(II) reacts with hydrogen in the presence of base to give the purple-colored monohydride HRuCl(PPh<sub>3</sub>)<sub>3</sub>.<ref>{{cite book|chapter=Chlorohydridotris(triphenylphosphine)ruthenium(II)|first1=R. A.|last1=Schunn|first2=E. R.|last2=Wonchoba|title=Inorganic Syntheses|page=131|doi=10.1002/9780470132449.ch26|volume=13|year=1972|isbn=9780470132449}}</ref> |
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:RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> + 2 CO → ''trans,trans,trans''-RuCl<sub>2</sub>(CO)<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub> + PPh<sub>3</sub> |
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:RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> + H<sub>2</sub> + NEt<sub>3</sub> → HRuCl(PPh<sub>3</sub>)<sub>3</sub> + Cl |
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Dichlorotris(triphenylphosphine)ruthenium(II) reacts with ] to produce the all trans isomer of dichloro(dicarbonyl)bis(triphenylphosphine)ruthenium(II). |
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This kinetic product isomerizes to the cis adduct during ]. ''trans''-RuCl<sub>2</sub>(dppe)<sub>2</sub> forms upon treating RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> with ]. |
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:RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> + 2 dppe → RuCl<sub>2</sub>(dppe)<sub>2</sub> + 3 PPh<sub>3</sub> |
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:RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> + 2 CO → ''trans,trans,trans''-RuCl<sub>2</sub>(CO)<sub>2</sub>(PPh<sub>3</sub>)<sub>2</sub> + PPh<sub>3</sub> |
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This kinetic product isomerizes to the cis adduct during ]. ''trans''-RuCl<sub>2</sub>(dppe)<sub>2</sub> forms upon treating RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> with ]. |
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:RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> + 2 dppe → RuCl<sub>2</sub>(dppe)<sub>2</sub> + 3 PPh<sub>3</sub> |
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RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> catalyzes the decomposition of ] into ] and ] gas in the presence of an ].<ref>{{cite journal| doi=10.1002/anie.200705972| title=Controlled Generation of Hydrogen from Formic Acid Amine Adducts at Room Temperature and Application in H2/O2Fuel Cells| year=2008| last1=Loges| first1=Björn| last2=Boddien| first2=Albert| last3=Junge| first3=Henrik| last4=Beller| first4=Matthias| journal=Angewandte Chemie International Edition| volume=47| issue=21| pages=3962–3965| pmid=18457345}}</ref> Since ] can be trapped and hydrogenated on an industrial scale, ] represents a potential storage and transportation medium. |
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==Use in organic synthesis== |
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==Use in organic synthesis== |
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RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> facilitates oxidations, reductions, cross-couplings, cyclizations, and isomerization. It is used in the ] of chlorocarbons to alkenes.<ref name=eEROS>Plummer, J. S.; Shun-Ichi, M.; Changjia, Z. “Dichlorotris(triphenylphosphine)ruthenium(II)”, ''e-EROS Encyclopedia of Reagents for Organic Synthesis'', '''2010''', John Wiley. {{DOI|10.1002/047084289X.rd137.pub2}}</ref> |
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RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> facilitates oxidations, reductions, cross-couplings, cyclizations, and isomerization. It is used in the ] of chlorocarbons to alkenes.<ref name=eEROS>Plummer, J. S.; Shun-Ichi, M.; Changjia, Z. "Dichlorotris(triphenylphosphine)ruthenium(II)", ''e-EROS Encyclopedia of Reagents for Organic Synthesis'', '''2010''', John Wiley {{doi|10.1002/047084289X.rd137.pub2}}</ref> |
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Dichlorotris(triphenylphosphine)ruthenium(II) serves as a precatalyst for the ] of ], ], ], ], and ]. On the other hand, it catalyzes the oxidation of alkanes to tertiary alcohols, amides to t-butyldioxyamides, and tertiary amines to α-(t-butyldioxyamides) using tert-butyl hydroperoxide. Using other peroxides, oxygen, and acetone, the catalyst can oxidize alcohols to aldehydes or ketones. Using dichlorotris(triphenylphosphine)ruthenium(II) the N-alkylation of amines with alcohols is also possible (see "]").<ref name=eEROS/> |
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Dichlorotris(triphenylphosphine)ruthenium(II) serves as a precatalyst for the ] of ], ], ], ], and ]. On the other hand, it catalyzes the oxidation of alkanes to tertiary alcohols, amides to t-butyldioxyamides, and tertiary amines to α-(t-butyldioxyamides) using tert-butyl hydroperoxide. Using other peroxides, oxygen, and acetone, the catalyst can oxidize alcohols to aldehydes or ketones. Using dichlorotris(triphenylphosphine)ruthenium(II) the N-alkylation of amines with alcohols is also possible (see "]").<ref name=eEROS/> |
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RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> efficiently catalyzes carbon-carbon bond formation from cross couplings of alcohols through C-H activation of sp3 carbons in the presence of a ].<ref>Shu-Yu, Z.; Yong-Qiang, T.; Chun-An, F.; Yi-Jun, J.; Lei, S.; Ke, C.; En, Z.; “Cross-Coupling Reactions between alcohols through sp<sup>3</sup> C-H Activation Catalyzed by a Ruthenium/Lewis Acid System” ''Chem. Eur. J.'', '''2008''', ''14'', 10201-10205. {{DOI|10.1002/chem.200801317}}</ref> |
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RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> efficiently catalyzes carbon-carbon bond formation from cross couplings of alcohols through C-H activation of sp<sup>3</sup> carbon atoms in the presence of a ].<ref>{{cite journal|doi=10.1002/chem.200801317|title=Cross-Coupling Reaction between Alcohols through sp<sup>3</sup> C−H Activation Catalyzed by a Ruthenium/Lewis Acid System|year=2008|last1=Zhang|first1=Shu-Yu|last2=Tu|first2=Yong-Qiang|last3=Fan|first3=Chun-An|last4=Jiang|first4=Yi-Jun|last5=Shi|first5=Lei|last6=Cao|first6=Ke|last7=Zhang|first7=En|journal=Chemistry - A European Journal|volume=14|issue=33|pages=10201–10205|pmid=18844197}}</ref> |
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RuCl<sub>2</sub>(PPh<sub>3</sub>)<sub>3</sub> efficiently catalyzes the decomposition of ] into ] and ] gas in the presence of an ].<ref>Loges, B.; Boddien, A.; Junge, H.; Beller, M., “Controlled Generation of Hydrogen from Formic Acid Amine Adducs at Room Temperature and Application in H<sub>2</sub>/O<sub>2</sub> Fuel Cells”, ''Angew. Chem. Int. Ed.'', '''2008''', ''47'', 3962-3965. {{DOI| 10.1002/anie.200705972}}</ref> Since ] can be trapped and hydrogenated on an industrial scale, ] represents a potential storage and transportation medium. |
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==References== |
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==References== |
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<references /> |
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<references /> |
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{{Ruthenium compounds}} |
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{{Ruthenium compounds}} |
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