70196-25-7

Upstream product

• 177283-23-7 Rh(η(3)-cyclooctenyl)(Ph2P(CH2)3PPh2) 
• 6737-42-4 1,3-bis-(diphenylphosphino)propane 
• 64-17-5 ethanol 
• 188970-75-4 Mg⁽²⁺⁾*Cl^(1-)*Rh((C₆H₅)2PCH₂CH₂CH₂P(C₆H₅)2)2^(1-)=[Rh((C₆H₅)2PCH₂CH₂CH₂P(C₆H₅)2)2]MgCl 
• 1333-74-0 hydrogen 

Downstream Products

• 37737-62-5 tris(catecholato)diboron 
• 150904-96-4 bis(1,3-bis(diphenylphosphino)propane)rhodium formate 
• 81524-37-0 RhH(CO)(C₆H₅)2PCH₂CH₂CH₂P(C₆H₅)2(C₆H₅)2P(CH₂)3P(C₆H₅)2 
• 86853-77-2 [Rh(CO)((C₆H₅)2PCH₂CH₂CH₂P(C₆H₅)2)]2(CO)2*0.5C₆H₆ 

Relevant academic research and scientific papers

'Grignard-analogous' rhodium phosphane complexes

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+.

CO2 activation. 7. Formation of the catalytically active intermediate in the hydrogenation of carbon dioxide to formic acid using the [{(COD)Rh(μ-H)}4]/ Ph2P(CH2)4PPh2 catalyst: First direct observation of hydride migration from rhodium to coordinated 1,5-cyclooctadiene

The nature of the catalytically active intermediate formed in situ from the tetrameric cluster [{(COD)Rh(μ-H)}4] (COD = 1,5-cyclooctadiene; 1) and the bidentate phosphane Ph2P(CH2)4PPh2 (dppb) during hydrogenation of CO2 to formic acid was investigated. Kinetic measurements suggest the initial formation of a catalyst precursor that reacts with dihydrogen to give the actual active species. NMR spectroscopic investigations of the reaction of 1 with dppb in THF-d8 reveal three phosphorus-containing products that were fully characterized by one- and two-dimensional techniques, including 2D-(31P,1H)-COLOC spectra. The tetrameric hydride cluster [{(dppb)Rh(μ-H)}4] (2) and the double-phosphane-substituted monomeric rhodium hydride [(dppb)2RhH] (3) are formed as byproducts in low yield. The (phosphane)rhodium η3-cyclooctenyl complex [(dppb)Rh(η3-C8H13)] (4), arising via hydride transfer from rhodium to coordinated COD, is the major product, containing about 80% of the dppb. Complex 4 was isolated from the mixture of products, and its molecular structure was determined by X-ray crystal diffraction. Hydrogenolysis of the allyl moiety in the presence of excess dppb was shown to yield 3 presumably via the 14e species [(dppb)RhH]. The results are most consistent with the formation of 4 as the actual precursor for the active species [(dppb)RhH] in the rhodium-catalyzed hydrogenation of CO2 to formic acid using in situ catalysts consisting of 1 and dppb.

MONO- AND DINUCLEAR RHODIUM CARBONYL SPECIES CONTAINING MONODENTATE OR BRIDGING 1,3-BIS(DIPHENYLPHOSPHINO)PROPANE

The interaction of 2(μ-CO)2 with H2 in CH2Cl2 in the presence of varying amounts of dpp leads mainly to catalytically important species which include Rh(H)CO)(dpp)(dpp*) and 2(μ-dpp), these being formed also by treating RhH(dpp)2 with about 2 equivalents of CO; dpp and dpp* = bidentate and monodentate 1,3-bis(diphenylphosphino)propane, respectively.Mechanistic pathways involving a detected RhH(CO)2(dpp) and a non-detected RhH(CO)(dpp) species are suggested.