Manipulation of Organolanthanide Coordinative Unsaturation. Synthesis, Structures, Structural Dynamics, Comparative Reactivity, and Comparative Thermochemistry of Dinuclear μ-Hydrides and μ-Alkyls with [μ-R2SiC(Me4C5)(C5H4)]2 Supporting Ligation

David Stern, Michal Sabat, Tobin Jay Marks*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

190 Scopus citations

Abstract

This contribution describes lutetium and yttrium hydrocarbyl and hydride chemistry based upon the chelating R2Si(η5C5H4)(η5Me4C5)2- ligand (R = Me, Et; abbreviated R2SiCpCp). The ligand is prepared by reaction of the corresponding R2Si(Cp)Cl derivative with NaC5H5. Subsequent metalation and reaction with MCI3-3THF (M = Y, Lu) yields R2SiCpCpMCI2-Li(OEt2)2+ complexes, which in turn can be alkylated to yield R2SiCpCp″ MCHTMS2 derivatives (TMS = SiMe3). Pertinent crystallographic data for Me2SiCpCp″ LuCHTMS2 at-120 °C: PI (no. 2), z = 4, a = 16.049 (3) A, b = 17.945 (4) A, c = 8.993 (3) A, a = 93.36 (2)°, s = 90.92 (2)°, and y = 82.54 (2)°; R(F) = 0.030 for 6085 independent reflections with I > 3σ(I). The structure is of a gbent-sandwich Cp-2MX-type (Cp- = η5-Me5C5) with relaxed interligand nonbonded interactions vis-a-vis the Cp'2M and Me2SiCp2M analogues (Lu-CHTMS2 = 2.365 (7) A) and having one close Lm-MeSi (Lu-C = 2.820 (8) A) secondary interaction. These alkyls initiate the polymerization of ethylene and undergo relatively slow hydrogenolysis to yield dihydrides of stoichiometry (R2SiCpCp″MH)2 via detectable intermediates of stoichiometry (R2SiCpCp)2M2(H)(CHTMS2). Pertinent crystallographic data for (Et2SiCpCpLuH)2 at-120°C: P2fn (no. 14), z = 2, a = 11.558 (3) A, b = 8.590 (2) A, c = 18.029 (3) A, s = 100.10 (2) A, R(F) = 0.022 for 2656 independent reflections with I > 3 (I). The structure has an idealized C2i, Lu(M-Et2SiCpCp)2-H)2Lu geometry with both bridging Et2SiCpCp and hydride ligands (Lu-H = 2.16 (4), 2.13 (4) A). These complexes react slowly (compared to monomeric Cp'2MH and Me2SiCp2MH), reversibly, and regiospecifically with α-olefins to form bridging alkyls of structure M(μ-R2SiCpCp)2(μ-H)(μ-R')M, R' = ethyl, n-propyl, n-hexyl. Pertinent crystallographic data for Lu-Et2SiCpCp)2(μ-H)(μ-CH3CH2)Lu at-120°C: P2Jc (no. 14), z = 6, a= 11.679 (4) A, 6 = 25.755 (5) A, c = 18.074 (2) A, s = 99.41 (2)°; R(F) = 0.058 for 4643 independent reflections with 1 > 3 (7). The Lu-Et2SiCpCp)2(μ-H)Lu framework is nearly identical to that in the dihydride above. The μ-ethyl fragment is bound very unsymmetrically with Lu-C(cr) = 2.46 (2) and 2.58 (2) A,. Lu-C(a)-C(/3) = 148 (1)° and 84.7 (5)°. In addition, Lu-C(η) = 2.78 (2) A suggests a strong secondary bonding interaction. Hydrogenolysis of the μ-alkyl linkages is considerably slower than for terminal alkyl bonds in Cp'2M(alkyl) and Me2SiCp2M(alkyl) complexes. NMR studies of the μ-alkyls reveal rapid rotation of the μ-alkyl ligands about the μ-μ-(H) vectors down to-85°C and rapid inversion at C(a) occurring with AG* = 12.5-13.5 kcal/mol (7C = +11-+39°C). Kinetic (rate law: v = A:[dihydride] [olefin]) and equilibration measurements reveal that the hydride addition process to 1-hexene (Et2SiCpCpLuH)2 + 1-hexene Lu(μ-Et2SiCpCp)2(μ-H)(μ-7-hexyl)Lu is described by AH =-10.7 (6) kcal/mol, AS =-25 (2) eu, AH* = 12.0 (4) kcal/mol, and AS* =-38.6 (7) eu. These results indicate that, in comparison to terminal bonding modes with similar metal ancillary ligation, lanthanide μ-ligands are kinetically deactivated with respect to olefin insertion (a rate depression of 10s. 1010), and μ-alkyl ligands are kinetically deactivated with respect to hydrogenolysis (a rate depression of 108-109). Moreover, relative to a bridging hydride ligand, lanthanide μ-alkyl coordination is found to be no more and probably less thermodynamically stable than terminal alkyl coordination.

Original languageEnglish (US)
Pages (from-to)9558-9575
Number of pages18
JournalJournal of the American Chemical Society
Volume112
Issue number26
DOIs
StatePublished - Jan 1 1990

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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