(Tricyclohexylphosphine)-(trifluoroacetato-O)-(2-((dimethylamino)methyl)phenyl-C,N)-palladium

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

C₂₉H₄₅F₃NO₂PPd

InChI=1/C18H33P.C9H12N.C2HF3O2.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;3-2(4,5)1(6)7;/h16-18H,1-15H2;3-6H,8H2,1-2H3;(H,6,7);/q;;;+1/p-1

Identification Number:	10.5258/ecrystals/37
Controlled Keywords:	Suzuki coupling and Buchwald-Hartwig amination reactions, activation of palladacyclic precatalysts
Date Created:	04 April 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.

Data collection parameters

Chemical formula	C29 H45 F3 N O2 P Pd
Crystal morphology
Crystal system	Monoclinic
Space group symbol	P2(1)/c
Cell length a	14.7341(2)
Cell length b	11.2352(2)
Cell length c	19.3377(3)
Cell angle alpha	90.00
Cell angle beta	111.8780(10)
Cell angle gamma	90.00
Data collection temperature	120(2)

Refinement results

Solution figure of merit
R Factor (Obs)	0.0284
R Factor (All)	0.0322
Weighted R Factor (Obs)	0.0714
Weighted R Factor (All)	0.0745

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/37)
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