Premium
Synthesis and Structural Characterization of Palladacycles with Polydentate Ligands by a Stepwise Coupling Route – Palladacycles Containing Halides as Efficient Catalysts and Substrates
Author(s) -
Xu Chen,
Wang ZhiQiang,
Zhang YaPeng,
Dong XinMing,
Hao XinQi,
Fu WeiJun,
Ji BaoMing,
Song MaoPing
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100617
Subject(s) - chemistry , denticity , halide , catalysis , amination , palladium , crystal structure , medicinal chemistry , coupling reaction , yield (engineering) , stereochemistry , crystallography , organic chemistry , materials science , metallurgy
A series of ferrocenyl palladacycles with polydentate ligands were conveniently prepared by the Suzuki coupling reactions of a halide‐containing ferrocenyl palladacycle [PdCl({(η 5 ‐C 5 H 5 )}Fe{(η 5 ‐C 5 H 3 )N 2 C 4 H 2 Cl})(PPh 3 )] ( 1 ) andarylboronic acids without additional palladium catalysis. In the absence of additional base, amination also occurred in high yield. This new protocol was successfully applied to the Suzuki coupling reactions of the analogous halide‐containing palladacycle [PdCl({(η 5 ‐C 5 H 5 )}Fe{(η 5 ‐C 5 H 3 )NC 5 H 3 Br})(PPh 3 )] ( 15 ) and Buchwald–Hartwig amination of the analogous complex [PdCl({(η 5 ‐C 5 H 5 )}Fe{(η 5 ‐C 5 H 3 )NC 5 H 3 Br})(DCPAB)] ( 32 ), where DCPAB = 2‐dicyclohexylphosphanyl‐2′‐( N , N ‐dimethylamino)biphenyl. The halide‐containing palladacycles act as efficient catalysts and substrates in the coupling reactions. 37 new examples have been fully characterized by elemental analysis, IR and 1 H NMR spectroscopy, and ESI‐MS. Additionally, the molecular structures of eight compounds were determined by single‐crystal X‐ray diffraction, and many types of intermolecular C–H ··· Cl (O, N, π) interactions and π–π interactions were found in the crystal structures of these palladacycles.