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Citation: Xuhu GUO, Chuntao ZHANG, Jinshu LI, Yuanyuan TAN, Qaiowen CHANG, Juan YU. Structure and catalytic performance of [Pd(1, 5-cyclooctadiene)X2] (X=Cl, Br) modulated by organophosphine ligands[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(6): 1247-1260. doi: 10.11862/CJIC.20250299 shu

Structure and catalytic performance of [Pd(1, 5-cyclooctadiene)X2] (X=Cl, Br) modulated by organophosphine ligands

  • Kunming Precious Metals Research Institute, National Key Laboratory of Precious Metal Functional Materials, Yunnan Precious Metals Lab Co., Ltd., Kunming 650106, China

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  • The chemical structure of palladium precursors and their synergistic interactions with ligands play a decisive role in regulating the configuration of in situ generated Pd(0) active species, thereby governing the efficiency of C—C coupling reactions. So, in this work, 1, 5-cyclooctadiene palladium halides, [Pd(COD)X2] (COD=1, 5-cyclooctadiene, X=Cl, Br), were employed as palladium precursors, and organophosphines (PR3) were introduced as regulatory ligands to systematically investigate their effects on catalytic performance in C—C coupling reactions. The structural characteristics and solvent stability of the Pd(Ⅱ) precursors were elucidated by elemental analysis, infrared spectroscopy, nuclear magnetic resonance spectroscopy, and density functional theory calculations. In combination with single-crystal X-ray diffraction analysis of catalyst-derived species after reaction, the structural evolution of the palladium precursor during catalysis was examined. The results demonstrate that PR3-regulated cis-[Pd(COD)X2]/Pd(0) catalytic systems exhibit significantly higher catalytic efficiency than the commercially available trans-[Pd(PPh3)2Cl2] system. The in situ generated electron-rich cis-(PR3)2Pd(0) species display enhanced nucleophilicity, which facilitates C—X bond activation and accelerates the oxidative addition step. A clear ligand-dependent trend in catalytic activity was observed in the order: cis-[Pd(COD)X2]/Xantphos > cis-[Pd(COD)X2]/PPh3 > trans-[Pd(PPh3)2 Cl2] > [Pd(COD)X2]. Mechanistic studies indicate that coordination of electron-rich phosphine ligands to Pd(0), together with steric hindrance effects, effectively suppresses palladium aggregation and deactivation. Furthermore, ligand-controlled configuration and halogen effects synergistically promote Pd(0) generation. The rigid backbone of Xantphos enforces cis coordination at the palladium center, affording highly active cis-(Xantphos)Pd(0) species with increased exposure of active sites, whereas intermediates derived from PPh3 readily form mixtures of cis and trans isomers. Halogen dependence was also evident (cis-[Pd(COD)Br2] > cis-[Pd(COD)Cl2]): the lower electronegativity of bromide increases electron density at the Pd(0) center, thereby improving resistance to oxidation and stabilizing the active species. In addition, the weaker Pd—Br bond facilitates the faster generation of Pd(0), leading to improved catalytic efficiency and higher product yields.
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    1. [1]

      ZHANG L X, ZHOU F B, CHENG G Y, YANG X, XIAO D D, JIANG D H, CHENG H C, YUAN B X, SHI J C. Synthesis and characterization of terphenyl phosphine ligands and their palladium catalyst precursors[J]. Organometallics, 2025, 44(15): 1653-1659  doi: 10.1021/acs.organomet.5c00129

    2. [2]

      WANG Z, ZHANG Z G, LU X Y. Effect of halide ligands on the reactivity of carbon-palladium bonds: Implications for designing catalytic reactions[J]. Organometallics, 2000, 19(5): 775-780  doi: 10.1021/om990670h

    3. [3]

      XIE H J, FAN T, LEI Q F, FANG W J. New progress in theoretical studies on palladium-catalyzed C—C bond-forming reaction mechanisms[J]. Sci. China Chem., 2016, 59(11): 1432-1447  doi: 10.1007/s11426-016-0018-2

    4. [4]

      ZHAN B B, JIN L, SHI B F. Palladium-catalyzed enantioselective C—H functionalization via C—H palladation[J]. Trends Chem., 2022, 4(3): 220-235  doi: 10.1016/j.trechm.2021.12.005

    5. [5]

      RAGO A J, DONG G. Synthesis of indoles, indolines, and carbazoles via palladium-catalyzed C—H activation[J]. Green Synth. Catal., 2021, 2(2): 216-227

    6. [6]

      TRZECIAK A M, WOJTKÓW W, ZIÓŁKOWSKI J J. Catalytic activity of palladium complexes, PdCl2(COD) and PdCl2(P(OPh)3)2, in methoxy-carbonylation of iodobenzene[J]. Inorg. Chem. Commun., 2003, 6(7): 823-826  doi: 10.1016/S1387-7003(03)00105-9

    7. [7]

      MOHANTY S, PUNJI B, BALAKRISHNA M S. Synthesis and reaction kinetics of Pd(1, 5-cyclooctadiene)Cl2 with N, N′-methylene-bis (2-aminopyridyl): An efficient catalyst for Suzuki-cross-coupling reactions[J]. Polyhedron, 2006, 25(3): 815-820  doi: 10.1016/j.poly.2005.08.013

    8. [8]

      FU G C. The development of versatile methods for palladium-catalyzed coupling reactions of aryl electrophiles through the use of P(t-Bu)3 and PCy3 as ligands[J]. Accounts Chem. Res., 2008, 41(11): 1555-1564  doi: 10.1021/ar800148f

    9. [9]

      FLECKENSTEIN C A, PLENIO H. Sterically demanding trialkylphosphines for palladium-catalyzed cross coupling reactions-alternatives to P(t-Bu)3[J]. Chem. Soc. Rev., 2010, 39(2): 694-711  doi: 10.1039/B903646F

    10. [10]

      WANG J R, XU B, WANG Y B, XIA G Z, ZHANG Z M, ZHANG J L. Pd-catalyzed enantioselective three-component carboamination of 1, 3-cyclohexadiene[J]. J. Am. Chem. Soc., 2024, 146(31): 21231-21238  doi: 10.1021/jacs.4c07382

    11. [11]

      SEECHURN C C C J, SPERGER T, SCRASE T G, SCHOENEBECK F, COLACOT T J. Understanding the unusual reduction mechanism of Pd(Ⅱ) to Pd(Ⅰ): Uncovering hidden species and implications in catalytic cross-coupling reactions[J]. J. Am. Chem. Soc., 2017, 139(14): 5194-5200  doi: 10.1021/jacs.7b01110

    12. [12]

      HUPPERICH D, PONCE-DE-LEÓN J, FUNES-ARDOIZ I, SPERGER T, SCHOENEBECKET F. Sterically induced acceleration of aryl halide activation by Pd(0): A radical alternative to 2-electron oxidative addition[J]. J. Am. Chem. Soc., 2025, 147(23): 19941-19948  doi: 10.1021/jacs.5c04407

    13. [13]

      SOLIN N, SZABÓ K J. Mechanism of the η3-η1-η3 isomerization in allylpalladium complexes: Solvent coordination, ligand, and substituent effects[J]. Organometallics, 2001, 20(25): 5464-5471  doi: 10.1021/om010793d

    14. [14]

      DEANGELIS A J, GILDNER P G, CHOW R, COLACOT T J. Generating active "L-Pd (0)" via neutral or cationic π-allylpalladium complexes featuring biaryl/bipyrazolylphosphines: Synthetic, mechanistic, and structure-activity studies in challenging cross-coupling reactions[J]. J. Org. Chem., 2015, 80(13): 6794-6813.  doi: 10.1021/acs.joc.5b01005

    15. [15]

      Shaughnessy K H. Development of palladium precatalysts that efficiently generate LPd(0) active species[J]. Isr. J. Chem., 2020, 60(3/4): 180-194

    16. [16]

      RETTIG M F, WING R M, WIGER G R. X-ray crystallographic, chemical, and spectroscopic studies of the palladium dichloride complexes of cyclonona-1, 5-diene, cycloocta-1, 5-diene, cycloocta-1, 4-diene, and cyclohepta-1, 4-diene[J]. J. Am. Chem. Soc., 1981, 103(11): 2980-2986  doi: 10.1021/ja00401a012

    17. [17]

      KLEIN A, DOGAN A, FETH M, BERTAGNOLLI H. Cyclooctadi-enemethylpalladium complexes: Synthesis, structures and reactivity[J]. Inorg. Chim. Acta, 2003, 343: 189-201  doi: 10.1016/S0020-1693(02)01231-8

    18. [18]

      STOCKLAND JR R A, ANDERSON G K, RATH N P, BRADDOCK W J, ELLEGOOD J C. Synthesis of the complexes [PdClR (cod)](R=benzyl, ethyl; cod=1, 5-cyclooctadiene). β-Elimination from [PdClEt(cod)] to give the η1, η2 and η3 isomers of [Pd2(μ-Cl)2(C8H13)2][J]. Can. J. Chem., 1996, 74(11): 1990-1997  doi: 10.1139/v96-226

    19. [19]

      POWELL D B, LEEDHAM T J. Infrared and Raman spectra of 1, 5-cyclooctadiene complexes of rhodium, palladium and platinum[J]. Spectroc. Acta Pt. A‒Molec. Biomolec. Spectr., 1972, 28(2): 337-341

    20. [20]

      KUNKELY H, VOGLER A. Electronic spectrum and photoreactivity of dichloro (1, 5-cyclooctadiene)-palladium(Ⅱ)[J]. J. Organomet. Chem., 1998, 559(1/2): 223-225

    21. [21]

      NEESE F. Software update: The ORCA program system, version 4.0[J]. Wiley Interdiscip. Rev. ‒Comput. Mol. Sci., 2018, 8(1): e1327  doi: 10.1002/wcms.1327

    22. [22]

      BECKE A D. Density-functional thermochemistry. Ⅲ. The role of exact exchange[J]. J. Chem. Phys., 1993, 98(7): 5648-5652  doi: 10.1063/1.464913

    23. [23]

      ARAVENA D, NEESE F, PANTAZIS D A. Improved segmented all-electron relativistically contracted basis sets for the lanthanides[J]. J. Chem. Theory Comput., 2016, 12(3): 1148-1156  doi: 10.1021/acs.jctc.5b01048

    24. [24]

      ŠTĚPNIČKA P, CÍSAŘOVÁ I. Crystal structure of dibromo (η4-1, 5-cyclooctadiene) palladium(Ⅱ)[J]. Collect. Czech. Chem. Commun., 1996, 61(9): 1335-1341  doi: 10.1135/cccc19961335

    25. [25]

      MOHANTY S, PUNJI B, BALAKRISHNA M S. Synthesis and reaction kinetics of Pd(1, 5-cyclooctadiene)Cl2 with N, N′-methylene-bis (2-aminopyridyl): An efficient catalyst for Suzuki-cross-coupling reactions[J]. Polyhedron, 2006, 25(3): 815-820  doi: 10.1016/j.poly.2005.08.013

    26. [26]

      STEPHENSON M D, HARDIE M J. Extended structures of transition metal complexes of 6, 7-dicyanodipyridoquinoxaline: π-Stacking, weak hydrogen bonding, and CN-π interactions[J]. Cryst. Growth Des., 2006, 6(2): 423-432  doi: 10.1021/cg050366t

    27. [27]

      MAGISTRATO A, PREGOSIN P S, ALBINATI A, ROTHLISBERGER U. The role of π-π stacking interactions in square planar palladium complexes. combined quantum mechanics/molecular mechanics QM/MM studies[J]. Organometallics, 2001, 20(20): 4178-4184  doi: 10.1021/om010485f

    28. [28]

      DATSENKO V P, NELYUBINA Y V, SMOL′YAKOV A F, LOGINOV D A. Cyclooctadiene iridium complexes [Cp*Ir(COD)X]+ (X=Cl, Br, I): Synthesis and application for oxidative coupling of benzoic acid with alkynes[J]. J. Organomet. Chem., 2018, 874: 7-12  doi: 10.1016/j.jorganchem.2018.08.014

    29. [29]

      HARTLEY F R. The cis- and trans-effects of ligands[J]. Chem. Soc. Rev., 1973, 2(2): 163-179  doi: 10.1039/cs9730200163

    30. [30]

      D′ALTERIO M C, CASALS-CRUAÑAS È, TZOURAS N V, TALARICO G, NOLAN S P, POATER A. Mechanistic aspects of the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction[J]. Chem. ‒Eur. J., 2021, 27(54): 13481-13493

    31. [31]

      JEDDI N, SCOTT N W J, FAIRLAMB I J S. Well-defined Pdn clusters for cross-coupling and hydrogenation catalysis: New opportunities for catalyst design[J]. ACS Catal., 2022, 12(19): 11615-11638  doi: 10.1021/acscatal.2c03345

    32. [32]

      SIVENDRAN N, PIRKL N, HU Z Y, DOPPIU A, GOOSSEN L J. Halogen-bridged methylnaphthyl palladium dimers as versatile catalyst precursors in coupling reactions[J]. Angew. Chem. ‒Int. Edit., 2021, 60(47): 25151-25160  doi: 10.1002/anie.202110450

    33. [33]

      CASADO A L, ESPINET P. On the configuration resulting from oxidative addition of RX to Pd(PPh3)4 and the mechanism of the cis-to-trans isomerization of [PdRX(PPh3)2] complexes (R=aryl, X=halide)[J]. Organometallics, 1998, 17(5): 954-959  doi: 10.1021/om9709502

    34. [34]

      PORTNOY M, MILSTEIN D. Chelate effect on the structure and reactivity of electron-rich palladium complexes and its relevance to catalysis[J]. Organometallics, 1993, 12(5): 1655-1664  doi: 10.1021/om00029a025

    35. [35]

      TOLMAN C A. Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis[J]. Chem. Rev., 1977, 77(3): 313-348

    36. [36]

      TATSUMI K, HOFFMANN R, YAMAMOTO A, STILLE J K. Reductive elimination of d8-organotransition metal complexes[J]. Bull. Chem. Soc. Jpn., 1981, 54(6): 1857-1867  doi: 10.1246/bcsj.54.1857

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