50396-26-4Relevant articles and documents
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
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.
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
