1339962-40-1

Basic information

• Product Name: [Rh(4,5-bis(diphenylphosphino)-9,9'-dimethylxanthene)I(CO)(Me)]BF₄
• CAS NO: 1339962-40-1
• Molecular Weight: 938.29
• Mol File: 1339962-40-1.mol
• Article Data: 1

Chemical Properties

• CAS DataBase Reference: [Rh(4,5-bis(diphenylphosphino)-9,9'-dimethylxanthene)I(CO)(Me)]BF₄(CAS DataBase Reference)
• NIST Chemistry Reference: [Rh(4,5-bis(diphenylphosphino)-9,9'-dimethylxanthene)I(CO)(Me)]BF₄(1339962-40-1)
• EPA Substance Registry System: [Rh(4,5-bis(diphenylphosphino)-9,9'-dimethylxanthene)I(CO)(Me)]BF₄(1339962-40-1)

Safety Data

• Hazardous Substances Data: 1339962-40-1(Hazardous Substances Data)

Upstream product

• 1339962-36-5 [Rh(acetyl)I(acetonitrile)(4,5-bis(diphenylphosphino)-9,9'-dimethylxanthene)]BF₄ 
• 1339962-38-7 [Rh(acetyl)I(CO)(4,5-bis(diphenylphosphino)-9,9'-dimethylxanthene)]BF₄ 
• 1241951-62-1 [Rh(CO)(4,5-bis(diphenylphosphino)-9,9'-dimethylxanthene)Cl] 
• 161265-03-8 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene 
• 367519-51-5 [Rh(CO)(4,5-bis(diphenylphosphino)-9,9'-dimethylxanthene)]BF₄ 
• 311-28-4 tetra-(n-butyl)ammonium iodide 
• 74-88-4 methyl iodide 

Relevant articles and documents

Mechanistic study of rhodium/xantphos-catalyzed methanol carbonylation

Rhodium/iodide catalysts modified with the xantphos ligand are active for the homogeneous carbonylation of methanol to acetic acid using either pure CO or CO/H2. Residues from catalytic reactions contain a Rh(III) acetyl complex, [Rh(xantphos)(COMe)I2] (1), which was isolated and crystallographically characterized. The xantphos ligand in 1 adopts a "pincer" κ3-P,O,P coordination mode with the xanthene oxygen donor trans to the acetyl ligand. The same product was also synthesized under mild conditions from [Rh(CO)2I]2. Iodide abstraction from 1 in the presence of donor ligands (L = MeCN, CO) gives the cationic acetyl species [Rh(xantphos)(COMe)I(L)]+, whereas in CH 2Cl2 migratory CO deinsertion gives [Rh(xantphos)(Me)I(CO) ]+ (4), which reacts with H2 to liberate methane, as observed in catalytic reactions using syngas. A number of Rh(I) xantphos complexes have been synthesized and characterized. Oxidative addition of methyl iodide to the cation [Rh(xantphos)(CO)]+ is very slow but can be catalyzed by addition of an iodide salt, via a mechanism involving neutral [Rh(xantphos)(CO)I] (6). IR spectroscopic data and DFT calculations for 6 suggest the existence in solution of conformers with different Rh-O distances. Kinetic data and activation parameters are reported for the reaction of 6 with MeI, which proceeds by methylation of the Rh center and subsequent migratory insertion to give 1. The enhancement of nucleophilicity arising from a Rh- - -O interaction is supported by DFT calculations for the SN2 transition state. A mechanism for catalytic methanol carbonylation based on the observed stoichiometric reaction steps is proposed. A survey of ligand conformations in xantphos complexes reveals a correlation between P-M-P bite angle and M-O distance and division into two broad categories with bite angle 143° (trans).