Structural and electronic effects of pentafluorophenyl substituents on cyclopentadienyl complexes of Fe, Co, Mn, and Re

被引:66
作者
Thornberry, M
Slebodnick, C
Deck, PA [1 ]
Fronczek, FR
机构
[1] Virginia Tech, Dept Chem, Blacksburg, VA 24061 USA
[2] Louisiana State Univ, Dept Chem, Baton Rouge, LA 70803 USA
关键词
D O I
10.1021/om000798v
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction of CpNa(Cp = C5H5) With C6F6 (diglyme, 110 degrees C, 14 h) afforded a mixture of products, from which two new triarylated cyclopentadienes, 1,2,4-Ar3C5H3 (3) and 1,2,3-Ar3C5H3 (4), were separated by silica gel chromatography (Ar = C6F5) The dienes 3 and 4 were readily converted (NaH, THF) to the corresponding triarylated sodium cyclopentadienides, (1,2,4-Ar3C5H2)Na (7) and (1,2,3-Ar3C5H2)Na (8). Reactions of the ligands 7 and 8 with FeBr2 afforded the ferrocenes (1,2,4-Ar3C5H2)(2)Fe (11) and (1,2,3-Ar3C5H2)2Fe (12), respectively. The cobaltocenes (ArC5H4)(2)CO (13), (1,3-Ar2C5H3)(2)CO (14), (1,2,4-Ar3C5H2)(2)CO (15), and (1,2,3-Ar3C5H2)(2)Co (16) were prepared from CoBr2 and (ArC5H4)Na (5), (1,3-Ar2C5H3)Na (6), 7, and 8, respectively. Oxidation of 13 lair, dilute aqueous HC1) followed by precipitation with KPF6 afforded [(ArC5H4)(2)Co](+)PFG(6)(-) (17). The homologous cobaltocenium ions [1,3-Ar2C5H3](2)Co+ (18), (1,2,4- Ar3C5H2)(2)Co+ (19), and (1,2,3-Ar3C5H2)(2)Co+ (20) were observed (NMR) only after dissolving the corresponding Co-II: species 14-16 in D2SO4; efforts to isolate 18-20 as hexafluorophosphates failed. Reactions of the ligands 5-8 with M(CO)(5)Br (M = Mn, Re) afforded the piano stool complexes (ArCp)Mn(CO)(3) (21), (1,8-Ar2Cp)Mn(CO)(3) (22), (1,2,4-Ar3C5H2)M(CO); (2, M =Mn; 27, M = Re), and (1,2,3-Ar3C5H2)M(CO)(3) (24, M = Mn; 28, M = Re). Both the voltammetric oxidation potentials (E-1/2) Of the substituted metallocenes 9-16 and the carbonyl stretching wavenumbers of the substituted piano stool complexes 21-24 and 25-28 increased linearly with increasing number of C6F5 substituents. Crystal structures were obtained for 2 (two polymorphs), 4, 11, 16, 23, 26, and 27. Noteworthy features of these structures include C6F5-C6F5 arene stacking, C6F5 stacking with benzene solvate molecules, C6F5 O dropC-M interactions, and extensive C-H F-C interactions. Barriers toward CP-C6F5 rotationand Cp-Fe-Cp rotation were quantified for several of the complexes using dynamic F-19 and H-1 NMR spectroscopy.
引用
收藏
页码:5352 / 5369
页数:18
相关论文
共 115 条
  • [31] Phenyl-perfluorophenyl stacking interactions: A new strategy for supermolecule construction
    Coates, GW
    Dunn, AR
    Henling, LM
    Dougherty, DA
    Grubbs, RH
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1997, 36 (03) : 248 - 251
  • [32] Tricarbonylrhenium(I) complexes of pentafluorophenyl-substituted indenyl ligands
    Deck, PA
    Fronczek, FR
    [J]. ORGANOMETALLICS, 2000, 19 (03) : 327 - 333
  • [33] Synthesis of pentafluorophenyl-substituted cyclopentadienes and their use as transition-metal ligands
    Deck, PA
    Jackson, WF
    Fronczek, FR
    [J]. ORGANOMETALLICS, 1996, 15 (25) : 5287 - 5291
  • [34] Synthesis and structural trends in pentafluorophenyl-substituted ferrocenes, 1,4-tetrafluorophenylene-linked diferrocenes, and 1,1′-ferrocenylene-1,4-tetrafluorophenylene co-oligomers
    Deck, PA
    Lane, MJ
    Montgomery, JL
    Slebodnick, C
    Fronczek, FR
    [J]. ORGANOMETALLICS, 2000, 19 (06) : 1013 - 1024
  • [35] DECK PA, 1999, SE REG M AM CHEM SOC
  • [36] DECK PA, 1998, 215 NAT M AM CHEM SO
  • [37] Doucet H, 1999, CHEM-EUR J, V5, P1320, DOI 10.1002/(SICI)1521-3765(19990401)5:4<1320::AID-CHEM1320>3.3.CO
  • [38] 2-R
  • [39] Hydrogen bonding in DNA - a return to the status quo
    Evans, TA
    Seddon, KR
    [J]. CHEMICAL COMMUNICATIONS, 1997, (21) : 2023 - 2024
  • [40] Evans WJ, 1999, ANGEW CHEM INT EDIT, V38, P1801, DOI 10.1002/(SICI)1521-3773(19990614)38:12<1801::AID-ANIE1801>3.0.CO