(Tricyclohexylphosphine)-(trifluoromethanesulfonato-O)-(2-((dimethylamino)methul)phenyl-C,N)-palladium

Sample Originator: Thomas Gelbrich, Michael B. Hursthouse, C. S. J. Cazin, R. B. Bedford, Peter N. Horton, Mark E. Light and Simon J. Coles.

C₂₈H₄₅F₃NO₃PPdS

InChI=1/C18H33P.C9H12N.CHF3O3S.Pd/c1-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;1-10(2)8-9-6-4-3-5-7-9;2-1(3,4)8(5,6)7;/h16-18H,1-15H2;3-6H,8H2,1-2H3;(H,5,6,7);/q;;;+1/p-1

Identification Number:	10.5258/ecrystals/35
Controlled Keywords:	High-Activity Catalysts for Suzuki Coupling and Amination Reactions with Deactivated Aryl Chloride Substrates: Importance of the Palladium Source
Date Created:	12 March 2002
Deposited On:	21 Jan 2008 15:28
Deposited By:	A.N. Admin

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.CCDC 207769

Data collection parameters

Chemical formula	C28 H45 F3 N O3 P Pd S
Crystal morphology
Crystal system	monoclinic
Space group symbol	P2(1)
Cell length a	9.2892(2)
Cell length b	9.6862(2)
Cell length c	16.7860(6)
Cell angle alpha	90.00
Cell angle beta	92.1110(10)
Cell angle gamma	90.00
Data collection temperature	120(2)

Refinement results

Solution figure of merit
R Factor (Obs)	0.0341
R Factor (All)	0.0420
Weighted R Factor (Obs)	0.0734
Weighted R Factor (All)	0.0772

Citation: Gelbrich, Thomas and Hursthouse, Michael B. and Cazin, C. S. J. and Bedford, R. B. and Horton, Peter N. and Light, Mark E. and Coles, Simon J. (2002) University of Southampton, Crystal Structure Report Archive. (doi:10.5258/ecrystals/35)
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