ChemInform Abstract The reaction of the Sm compound (I) with an excess of AlMe3 (II) yields the binuclear title complex (III). THF cleaves the bridging AlMe4 units in (III) liberating AlMe3 and the mononuclear title complex (V). The structures of (III) (space group P21/n, Z=2) and (V) (Pnma, Z=4) are determined by X-ray analysis. (V) reacts with aromatic and aliphatic hydrocarbons including benzene, toluene, hexane, cyclohexanes, cyclooctane liberating methane via net activation of C-H bonds. With toluene e.g. the benzyl derivative (VII) is formed. The methane generated in the reactions of (V) with deuterated substrates is CH4, which suggests that intramolecular formation of a spectroscopically undetected intermediate containing a metalated C5Me5 ring may occur before intermolecular reaction with the C-H bond. (V) metalates pyridine-d5 to form CH3D, reacts with Et2O to give the ethoxo derivative of (V), and reacts with H2 to form ((C5Me5)2Sm(µ-H))2. Both (III) and (V) polymerize ethylene.

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Synthesis and Reactivity of the Cationic Organosamarium(III) Complex [(C5Me5)2Sm(THF)2][BPh4], Including the Synthesis and Structure of a Metallocene with an Alkoxy-Tethered C5Me5 Ring, (C5Me,)2Sm[0(CH2)4C5Me5](THF)1

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A series of group 4 and group 5 metal aryloxide compounds containing enamidolate or enediamide ligation have been prepared by the intramolecular coupling of ?;2-acyl and 7)2-iminoacyl functional groups. For the group 4 metals reaction of the mono-iminoacyl's (ArO^M^-R'NCRXR) (M = Ti, Ar = 2,6-diisopropylphenyl, R = CH2Ph; M = Zr, Ar = 2,6-di-íerz-butylphenyl, R = CH2Ph) with carbon monoxide (700-1000 psi) leads directly to the corresponding enamidolate (1) with no evidence for the presumed intermediate mixed acyl, iminoacyl compound. However, the isolable bis ?;2-immoacyl compounds (ArO)2M(?;2-R'NCR)2 (M = Ti, Zr, Hf; ArO = 2,6-diisopropyl-, 2,6-diphenyl-, and 2,6-di-íe/7-butylphenyl; R = CH3, CH2Ph) only undergo intramolecular coupling to the corresponding enediamide derivatives (II) on thermolysis in hydrocarbon solvents.In contrast, attempts to prepare a bis qMminoacyl derivative of Ti(OAr-2,6-Ph2)2(r;2-PhNCCH2SiMe3)(CH2SiMe3) (OAr-2,6Ph2 = 2,6-diphenylphenoxide) by addition of PhNC led only to the isolation of a tris-inserted, coupled complex Ti(OAr-2,6Ph2)2[PhNCR=C(CR=NPh)NPh] (III) (R = CH2SiMe3) containing an enediamide chelate with an ¡mine substituent on the carbon backbone. The tantalum bis r;2-iminoacyl Ta(OAr-2,6Me2)3(j;2-xyNCCH2Ph)2 undergoes the clean formation of the enediamide Ta(OAr-2,6Me2)3[xyNC(CH2Ph)=C(CH2Ph)Nxy] (IV) on thermolysis at 110 °C. Single-crystal X-ray diffraction studies on six compounds of types I, II, III, and IV have been carried out. In the enamidolate compounds Ti(OAr-2,6Pri2)2[OC(CH2Ph)=C(CH2Ph)NBu'] (la) and Zr(OAr-2,6Bu'2)2[OC(CH2Ph)=C-(CH2Ph)Nxy] (lb) both molecules were found to contain a pseudotetrahedral geometry about the metal. The 5-membered