50396-26-4Relevant academic research and scientific papers
Rhodium-catalyzed branched-selective alkyne hydroacylation: A ligand-controlled regioselectivity switch
Gonzalez-Rodriguez, Carlos,Pawley, Rebekah J.,Chaplin, Adrian B.,Thompson, Amber L.,Weller, Andrew S.,Willis, Michael C.
supporting information; experimental part, p. 5134 - 5138 (2011/06/26)
It's all in the ligand: By choice of the appropriate diphosphine ligand a previously linear-selective alkyne hydroacylation process can be "switched" to be highly branched-selective (see scheme, l=linear, b=branched). Structural data for the ortho-iPr-dpp
Structure of diiodine adducts of some di- and tri-tertiaryphosphines in the solid state and in solution
Bricklebank, Neil,Godfrey, Stephen M.,McAuliffe, Charles A.,Deplano, Paula,Mercuri, Marie L.,Sheffield, Joanne M.
, p. 2379 - 2382 (2007/10/03)
A series of ditertiaryphosphine-tetraiodine adducts R2P(I2)(CH2)nP(I2)R 2 (R = Ph, n = 1-4; R = PhCH2 or o-CH3C6H4, n = 2) and two tritertiaryphosphine-hexaiodine adducts, PhP(CH2CH2PPh2)2I6 and CH3C(CH2-PPh2)3I6 have been prepared and characterised by 31P-{H} solution NMR and Raman spectroscopy. In the case of Ph2P(I2)(CH2)nP(I 2)Ph2 (n = 2 or 4), 31P-{H} NMR magic angle spinning NMR spectroscopy has been used to investigate the nature of the compounds in the solid state. In agreement with our previous extensive studies on the monophosphine derivatives, R3PI2, the tetraiododiphosphine compounds Ph2P(I2)(CH2)nP(I 2)Ph2 (n = 2 or 4) isolated from diethyl ether contain molecular four-co-ordinate phosphorus centres onto which the diiodine is bound as a linear spoke, as indicated by their 3IP-{H} NMR shifts obtained in CDCl3 solution. Again, in agreement with our previous solution studies of the monophosphine derivatives R3PI2, the diphosphine-tetraiodine adducts completely ionise in CDCl3 solution to produce the ionic compounds [R2P(I)(CH2)nP(I)R2]2I; the solution 31P-{H} NMR shifts are very similar to analogous solution shifts previously assigned to [R3PI]I. The Raman band assignable to v(P-I) has been identified for the compounds and a further band at lower frequency has been observed and assigned to v(I-I). Although the solid-state NMR spectra of the triphosphine-hexaiodine adducts were not recorded, a band assignable, to v(I-I) was observed in the Raman spectrum, suggesting the molecular four-co-ordinate spoke structure also prevails for these hexaiodotritertiaryphosphine compounds in the solid state. From solution 31P-{H} NMR shifts these adducts also appear to ionise in CDCl3 solution.
Electron withdrawing substituents on equatorial and apical phosphines have opposite effects on the regioselectivity of rhodium catalyzed hydroformylation
Casey, Charles P.,Lin Paulsen, Evelyn,Beuttenmueller, Eckart W.,Proft, Bernd R.,Petrovich, Lori M.,Matter, Brock A.,Powell, Douglas R.
, p. 11817 - 11825 (2007/10/03)
The electronic effects of electron withdrawing aryl substituents on equatorial and apical diphosphines were investigated. Chelating diphosphines designed to coordinate in diequatorial or in apical-equatorial positions were synthesized, and their effects on the regioselectivity of rhodium catalyzed 1-hexene hydroformylation were observed, Only diequatorial coordination was observed for 2,2'-bis[(diphenylphosphino)methyl]-1,1'-biphenyl (BISBI) complexes (BISBI)Ir(CO)2H (8) and [BISBI-(3,5-CF3)]Ir(CO)2H (10), and only apical-equatorial coordination was seen for 1,2-bis(diphenylphosphino)ethane (DIPHOS) complexes (DIPHOS)Ir(CO)2H (14) and [DIPHOS-(3,5-CF3)]Ir(CO)2H (15). For the trans-1,2-bis[(diphenylphosphino)methyl]cyclopropane (T-BDCP) complexes, a mixture of diequatorial and apical-equatorial complexes was seen. For (T-BDCP)Ir(CO)2H (12), 12-ae was favored over 12-ee by 63:37, but for [T-BDCP-(3,5-CF3)]Ir(CO)2H (13) the conformational preference was reversed and a 10:90 ratio of 13-ae:13-ee was seen. The electron withdrawing groups in the equatorial positions of BISBI-(3,5-CF3) (1) and T-BDCP-(3,5-CF3) (2) led to an increase in n-aldehyde regioselectivity in rhodium catalyzed hydroformylation. However, electron withdrawing aryl substituents in the apical positions of DIPHOS-(3,5-CF3) (3) led to a decrease in n-aldehyde regioselectivity in rhodium catalyzed hydroformylation.
The Preparation and Properties of Some Diposphines R2PCH2CH2PR2 (R = Alkyl or Aryl) and of their Rhenium(I) Dinitrogen Derivatives
Chatt, Joseph,Hussain, Wasif,Leigh, G. Jeffery,Ali, Hapipah Mohd.,Pickett, Christopher J.,Rankin, Douglas A.
, p. 1131 - 1136 (2007/10/02)
The synthesis of a range of diphosphines R2PCH2CH2PR2 from Cl2PCH2CH2PCl2 is described.The properties of a series of complexes derived from them are discussed.The relationship between the values of E1/2ox an
SYNTHESIS AND PHYSICAL PROPERTIES OF CHLORODI(o-TOLYL)PHOSPHINE, LITHIUM DI(o-TOLYL)PHOSHIDE AND THE DIPHOSPHINE SERIES (o-TOLYL)2P(CH2)NP(o-TOYLYL) (n =1-4, 6,8)
Clark, Peter W.,Mulraney, Bernard J.
, p. 51 - 59 (2007/10/02)
The starting material chlorodi(o-tolyl)phosphine has been prepared by the reaction of phosphorus trichloride and the Grignard of o-chlorotoluene.The intermediate lithium di(o-tolyl)phosphide was obtained by the direct reaction of lithium metal and chlorod
