Sample Originator: C. S. J. Cazin, R. B. Bedford, Michael B. Hursthouse, Thomas Gelbrich, Peter N. Horton, Mark E. Light and Simon J. Coles.
C15H21F3N2O3Pd
InChI=1/2C9H12N.2C4H8NO.2C2HF3O2.2Pd/c2*1-10(2)8-9-6-4-3-5-7-9;2*1-3-6-4-2-5-1;2*3-2(4,5)1(6)7;;/h2*3-6H,8H2,1-2H3;2*1-4H2;2*(H,6,7);;/q;;2*-1;;;2*+2/p-2
| Identification Number: | 10.5258/ecrystals/41 |
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| Controlled Keywords: | high-activity catalysts, Suzuki Coupling, amination reactions, deactivated aryl chloride substrates |
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| Date Created: | 09 May 2002 |
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| Deposited On: | 21 Jan 2008 15:28 |
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| Deposited By: | A.N. Admin |
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Depositor Comments
A range of ortho-metalated catalysts with alkylphosphine ligands of the general formula [Pd(X)(2N,C-C6H4CH2NMe2)(PR3)] have been synthesized, and the crystal structures of five examples (R = Cy, X = TFA, OTf, Cl, I; PR3 = PCy2(o-biphenyl), X = TFA) have been determined. The crystal structures of two dimeric precursor complexes, [{Pd(-TFA)(2N,C-C6H4CH2NMe2)}2] and [{Pd(TFA)(2N,C-C6H4CH=NiPr)}2], have also been determined. The application of the phosphine adducts to both Suzuki coupling and Buchwald-Hartwig amination reactions with aryl chloride substrates was examined, and the performance of these catalysts versus conventional palladium sources was evaluated. In general the palladacyclic complexes show considerably enhanced activity. Typically, the best activity is seen with tricyclohexylphosphine adducts in Suzuki coupling and tri-tert-butylphosphine analogues in amination reactions. In nearly all the amination reactions performed, small amounts of a second product species were observed, namely 4,6-bis(aryl)-3,4-dihydro-2H-[1,4]oxazines. The crystal structure of one example, 4,6-bis(4-methoxyphenyl)-3,4-dihydro-2H-[1,4]oxazine, was determined. Studies on the activation of palladacyclic precatalysts in the coupling of morpholine led to the isolation of a morpholine adduct, [Pd(TFA)(2N,C-C6H5CH2NMe2){NH(CH2CH2)O}], which was structurally characterized by X-ray analysis.DOI: 10.1021/om020841+
Data collection parameters
| Chemical formula | C15 H20 F3 N2 O3 Pd |
| Crystal morphology | |
| Crystal system | Monoclinic |
| Space group symbol | P2(1)/c |
| Cell length a | 9.3727(9) |
| Cell length b | 19.1440(15) |
| Cell length c | 20.2492(19) |
| Cell angle alpha | 90.00 |
| Cell angle beta | 101.41 |
| Cell angle gamma | 90.00 |
| Data collection temperature | 120(2) |
Refinement results
| Solution figure of merit | |
| R Factor (Obs) | 0.0535 |
| R Factor (All) | 0.0682 |
| Weighted R Factor (Obs) | 0.1097 |
| Weighted R Factor (All) | 0.1147 |
Citation: Cazin, C. S. J. and Bedford, R. B. and Hursthouse, Michael B. and Gelbrich, Thomas and Horton, Peter N. and Light, Mark E. and Coles, Simon J. (2002) University of Southampton, Crystal Structure Report Archive. (doi:10.5258/ecrystals/41)
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