15043-47-7Relevant academic research and scientific papers
Synthesis and characterization of [Rh(PP)(PP)]X complexes (PP = DPPE or DPPP, X = Cl? or BF4-). Phosphine exchange and reactivity in transfer hydrogenation conditions
Mannu, Alberto,Vlahopoulou, Gina,Kubis, Christoph,Drexler, Hans-Joachim
supporting information, p. 59 - 64 (2019/02/20)
The synthesis of heteroleptic monomeric cationic Rh(I) bis-diphosphine complex [Rh(dppe)(dppp)]Cl (dppe = 1,2-bis-(diphenylphosphino)ethane and dppp = 1,3-bis-(diphenylphosphino)propane) was achieved by reaction between the neutral dimeric complex [Rhsub
Rhodium-Catalyzed Insertion Reaction of PhP Group of Pentaphenylcyclopentaphosphine with Acyclic and Cyclic Disulfides
Arisawa, Mieko,Sawahata, Kyosuke,Yamada, Tomoki,Sarkar, Debayan,Yamaguchi, Masahiko
, p. 938 - 941 (2018/02/23)
Organophosphorus compounds with a phosphorus atom attached to a phenyl group and two organothio/organoseleno groups were synthesized using the rhodium-catalyzed insertion reaction of the PhP group of pentaphenylcyclopentaphosphine (PhP)5 with acyclic disulfides and diselenides. The method was applied to the synthesis of heterocyclic compounds containing the S-P-S group by the reaction of (PhP)5 and cyclic disulfides such as 1,2-dithietes, 1,2-dithiocane, 1,4,5-dithiopane, and 1,2-dithiolanes.
Double hydrophosphination of alkynes promoted by rhodium: The key role of an N-heterocyclic carbene ligand
Di Giuseppe, Andrea,De Luca, Roberto,Castarlenas, Ricardo,Pérez-Torrente, Jesús J.,Crucianelli, Marcello,Oro, Luis A.
supporting information, p. 5554 - 5557 (2016/05/09)
The regioselective double hydrophosphination of alkynes mediated by rhodium catalysts is presented. The distinctive stereoelectronic properties of the NHC ligand prevent the catalyst deactivation by diphosphine coordination thereby allowing for the closing of a productive catalytic cycle.
Boron-boron bond oxidative addition to rhodium(I) and iridium(I) centres
Clegg, William,Lawlor, Fiona J.,Marder, Todd B.,Nguyen, Paul,Norman, Nicholas C.,Orpen, A. Guy,Quayle, Michael J.,Rice, Craig R.,Robins, Edward G.,Scott, Andrew J.,Souza, Fabio E. S.,Stringer, Graham,Whittell, George R.
, p. 301 - 309 (2007/10/03)
The reaction between the diborane(4) compound B2(1,2-O2C6H4)2 and either of the rhodium(I) complexes [RhCl(PPh3)3] or [{Rh(μ-Cl)(PPh3)2}2] afforded the colourless rhodium(III) bis(boryl) species [RhCl(PPh3)2-{B(1,2-O2C6H 4)}2]. Similar reactions have been carried out with the diborane(4) compounds B2(1,2-O2-4-ButC6H3) 2, B2(1,2-O2-3,5-But2C 6H2)2, B2(1,2-O2-3-MeC6H3)2, B2(1,2-O2-4-MeC6H3)2, B2(1,2-O2-3-MeOC6H3)2, B2(1,2-S2C6H4)2, B2(1,2-S2-4-MeC6H3)2 and B2[R,R-1,2-O2CH(CO2Me)CH(CO 2Me)]2 affording analogous rhodium complexes all of which have been characterised spectroscopically. The complexes derived from the reactions with B2(1,2-O2C6H4)2 and B2(1,2-O2-3-MeC6H3)2 have also been characterised by X-ray crystallography, the structures comprising a five-co-ordinate rhodium centre with a square-based-pyramidal geometry in which the apical site is occupied by a boryl group and the phosphines are mutually trims in basal positions. Reactivity studies have also been carried out for [RhCl(PPh3)2{B(1,2-O2C6H 4)}2]. Hydrolysis or alcoholysis with catechol afforded [RhH2Cl(PPh3)3] and either B2(1,2-O2C6H4)2(μ-O) or B2(1,2-O2C6H4)3 and addition of the phosphines PMe3, PEt3 and PMe2Ph afforded the new bis(boryl) compounds cis,mer-[RhCl(PMe3)3{B(1,2-O2C 6H4)}2], [RhCl(PEt3)2-{B(1,2-O2C6H 4)}2] and cis,mer-[RhCl(PMe2Ph)3{B(1,2-O2C 6H4)}2], the PEt3 complex having been characterised by X-ray crystallography and shown to be similar to the PPh3 complex. The iridium analogue [IrCl(PEt3)2-{B(1,2-O2C6H 4)}2] was also prepared from the reaction between [IrCl(PEt3)3] and B2(1,2-O2C6H4)2 and shown by X-ray crystallography to be isomorphous with the rhodium complex. Reactions between [RhCl(PPh3)2-{B(1,2-O2C6H 4)}2] and the phosphines PPri3, P(C6H11)3, 1,2-bis(diphenylphosphino)ethane (dppe) and 1,2-bis(dicyclohexylphosphino)ethane (dcpe) are also described although these do not result in new rhodium boryl complexes. The reaction between [{RhCl(dppe)}2] and B2(1,2-O2C6H4)2 afforded a compound tentatively assigned as [Rh(dppe)2{B(1,2-O2C6H4)}] with analogous compounds being formed with the diborane(4) compounds B2(1,2-O2-3-MeC6H3)2 and B2(1,2-O2-4-MeC6H3)2. Finally, the reaction between [Rh(PMe3)4]Cl and the diborane(4) compound B2(1,2-O2C6H4)2 is described which affords cis,mer-[RhCl(PMe3)3{B(1,2-O2C 6H4)}2]. Analogous reactions with B2(1,2-O2-3,5-But2C 6H2)2, B2(1,2-O2-3-MeC6H3)2 and B2[R,R-1,2-O2CH(CO2Me)CH-(CO 2MeJ]2 afforded similar products.
'Grignard-analogous' rhodium phosphane complexes
Bogdanovic,Leitner,Six,Wilczok,Wittmann
, p. 502 - 504 (2008/10/09)
Interesting stoichiometric and catalytic reactions are possible with the rhodium phosphane complexes [{Ph2P(CH2)(n)PPh2)(n)}2Rh][MgC1] (1: a, n = 2; b, n = 3), which are readily accessible by reaction of the chloride complexes 2 with active magnesium. The 'Grignard-analogous' compounds 1 react to form 3 (E = H, Me SiMe3) by protolysis, alkylation, and silylation. The interconversion of complexes 2a and 1a can be used for catalytic transfer of two electrons from magnesium to CO2 to yield CO and CO3/2+.
High-pressure NMR study of imine hydrogenation catalyzed by rhodium(I)/phosphine complexes. Characterization of species present under catalytic conditions
Ball, Graham E.,Cullen, William R.,Fryzuk, Michael D.,Henderson, William J.,James, Brian R.,MacFarlane, Kenneth S.
, p. 1464 - 1468 (2008/10/08)
A high-pressure NMR cell based upon the use of a sapphire NMR tube and simple valve design was constructed. The use of the cell to study the hydrogenation of imines under 1000-2000 psi of hydrogen mediated by [tertiary bis(phosphine)]rhodium(I) catalysts is described. Complexes of the type [{Rh(diphos)}2(μ-H)(μ-X)] (X = Cl, I, OMe), which are formed at these elevated hydrogen pressures, were characterized in situ, and the possible significance of these complexes in the catalysis is discussed. The dihydride cis-[RhH2(diphos)2]Cl, produced in a side reaction, was spectroscopically characterized at low temperature under 1200 psi of H2.
Conversion of N-allylaniline promoted by Rh(I): Synthesis and molecular structure of 2-ethyl-1,2,3,4-tetrahydro-3-methyl-4-anilinoquinoline
Aresta, Michele,Quarante, Eugenio,Treglia, Sonia,Ibers, James A.
, p. 577 - 583 (2008/10/08)
N-Allylaniline (1) is converted catalytically into 2-ethyl-1,2,3,4-tetrahydro-3-methyl-4-anilinoquinoline (7) by Rh(I). The first step of the N-heterocycle ring synthesis is the isomerization of 1 into trans-N-prop-1-enylaniline (3). The cis isomer could be neither isolated nor detected in the reaction mixture. 1 and 3 undergo an intermolecular double-bond addition reaction promoted by Rh(I) to afford (Z)-2-methyl-1,3-dianilinopent-1-ene (6). A rhodium complex containing 6 as a chelate was isolated in combination with other complexes, and the diamine was displaced and characterized. The ring closure reaction to afford 7 goes most probably through ortho metalation of a phenyl ring. The nature of 7 was established from a single-crystal X-ray study; the molecular structure of 7 in solution was determined by NMR spectroscopy.
Carbene Complexes. Part 18. Synthetic Routes to Electron-rich Olefin-derived Monocarbenerhodium(I) Neutral and Cationic Complexes and their Chemical and Physical Properties
Doyle, Michael J.,Lappert, Michael F.,Pye, Peter L.,Terreros, Pilar
, p. 2355 - 2364 (2007/10/02)
Electron-rich olefins of general type C(NR)CH2CH2NR>2 (LR2; R=Me, Et, Ph, 4-MeC6H4. 4-MeOC6H4, or 2-MeOC6H4) undergo reaction with a variety of rhodium(I) precursors via ligand displacement or chloride-bridge cleavage to afford monocarbenerhodium(I) complexes, such as R)(PPh3)2>, R)>, or R)(PPh3)>>LR= =C(NR)CH2CH2NR, cod=cyclo-octa-1,5-diene>; complexes Me)(PPh3)X> Me= =CN(Me)CH2CH2CH2NMe, X= CO or PPh3> have similarly,been obtained from the olefin L'Me2.From these, further complexes may be obtained by ligand (neutral or anionic) exchange processes : trans-R(PPh3)2>, trans-R)(PPh3)2>X (X=Br, Cl, ClO4, or I), R)(PPh3)> (X=BH4 or ClO4), cis-R)> (X=Cl or NO3), R)> (X= CH2SiMe3, ClO4, or NO3), cis-R)(PPh3)>, and R)>.In many of the reactions some of these ligand displacements at RhI proceed without retention of stereochemistry and it is likely that the observed product is the thermodinamically preferred isomer.Other chemical properties of the monocarbenerhodium(I) complexes relate to (i) rare examples of the displacement of LR from Rh by PPh3 or Ph2PCH2CH2PPh2 under rather forcing conditions, and (ii) oxidative addition (not particularly facile) of HCl, Cl, or C2(CN)4.The 45 new complexes heva been characterised by analysis and spectroscopy (i.r. and 1H and 31P n.m.r.) and, where appropriate, relative molecular mass determination , and electrical conductivity.From J(31P-103Rh) coupling constants it is concluded that LR has a greater trans influence than PPh3 but a lower cis influence.
Disulfur and diselenium complexes of rhodium and iridium
Ginsberg,Lindsell,Sprinkle,West,Cohen
, p. 3666 - 3681 (2008/10/08)
Coordinatively unsaturated low-valent rhodium and iridium complexes cleave S8 and Se8 rings and form complexes with the fragments. With square-planar [M(L-L)2]Cl (M = Rh, Ir; L-L = (C6H5)2PCH2CH2P(C 6H5)2 (dppe), (CH3)2PC-H2CH2P(CH3) 2 (dmpe)) this reaction affords the monomeric electrolytes [M(Y2)(L-L)2]Cl (Y2 = S2, Se2). Oligomeric compounds are obtained from the reactions with IrX(CO)(EPh3)2 and RhX(EPh3)3 (X = Cl, Br; E = P, As); the products are [{Ir(Se2)X(CO)(PPh3)}3], [{Ir(Se2)Cl(CO)(AsPh3}3], [{IrS6Cl(CO)(PPh3)2}n], [{RhS3X(PPh3)4}], [{RhSe3Cl(PPh3)}4], and [{RhY2Cl(AsPh3)}n] (Y2 = S2, Se2). In the compounds [M(Y2)(L-L)2]Cl, disulfur and diselenium are side-on bonded to the metal at equatorial positions of a distorted octahedron. An X-ray structure determination of the diselenium complex [Ir(Se2)(dppe)2]Cl·H2O·0.5C 6H6 shows the cation to be very similar to its dioxygen and disulfur analogues. The Se-Se distance is 2.312 (3) A?, about the same as the bond length in Se8 and 0.16 A? longer than the Se-Se bond in the free Se2 molecule. [M(Y2)(L-L)2]+ complexes have ν(S-S) at 510-550 cm-1 and ν(Se-Se) at 300-310 cm-1. The lowest energy feature of their electronic absorption spectra is a weak (ε 40-100 M-1 cm-1) band assigned as an a2π⊥* → b1 intraligand transition. 193Ir(1/2+ → 3/2 +) Mo?ssbauer spectra of [Ir(Y2)(dppe)2]Cl give isomer shifts that decrease along the series Y2 = O2, S2, Se2, in parallel with decreasing Y2 electronegativity. The disulfur or diselenium group in [M(Y2)(L-L)2]+ is readily reduced: mercury and tertiary phosphines strip sulfur or selenium from the complex with formation of HgS or HgSe and R3PS or R3PSe; the rate is very sensitive to the electronic environment of the disulfur or diselenium group and to the basicity of the phosphine. Low-valent group 8 metal complexes undergo oxidative addition across the S-S or Se-Se bond, allowing synthesis of the heterometallic (μ-S)2 dimers [(dppe)2Ir(μ-S)2PtL2]X (L = PPh3, X = Cl; L = PEtPh2, X = PF6) and [(dmpe)2Rh(μ-S)2Pt(PPh3)2]Cl, as well as the asymmetric dimer [(dppe)2Ir(μ-Se)2IrCl(CO)(PEt2Ph) 2]Cl. Oxidative addition together with displacement of [M(L-L)2]+ by excess of the addend complex also occurs, giving homometallic (μ-S)2 or (μ-Se)2 dimers such as [{Ir(μ-Se)Cl(CO)(PEt2Ph)2}2]. Iodine adds across the S-S bond of [Ir(S2)(dppe)2]Cl to form the novel cis-octahedral complex [Ir(SI)2(dppe)2]Cl.
