Search results for "Agostic interaction"
showing 5 items of 5 documents
Hydroxo Hydrido Complexes of Iron and Cobalt (Sn−Fe−Sn, Sn−Co−Sn): Probing Agostic Sn⋅⋅⋅H−M Interactions in Solution and in the Solid State
2000
Bis(toluene)iron 9 reacts with Lappert's stannylene [Sn[CH(SiMe3)2]2] (4) to form the paramagnetic bis-stannylene complex [[(eta6-toluene)Fe-Sn-[CH(SiMe3)2]2]2] (10). Compound 10 reacts with H2O to form the hydroxo hydrido complex [(eta6-C7H8)(mu-OH)(H)-Fe-[Sn[CH(SiMe3)2]2]2] (12) in high yield; its solid-state structure has been elucidated by X-ray and neutron diffraction analysis. In agreement with the 1H NMR results, 12 contains a hydridic ligand whose exact coordination geometry could be determined by neutron diffraction. The 1H and 119Sn NMR analysis of 12 suggested a multicenter Sn/Sn/H/Fe bonding interaction in solution, based on significantly large values of J(Sn,H,Fe) = 640+/-30 Hz…
Dimeric n-Alkyl Complexes of Rare-Earth Metals Supported by a Linked Amido−Cyclopentadienyl Ligand: Evidence for β-Agostic Bonding in Bridging n-Alk…
2002
The dimeric rare-earth hydrides [Ln(η^5:η^1-C_5Me_4SiMe_2NCMe_3)(THF)(μ-H)]_2 (Ln = Y, Yb) react with excess α-olefin H_2C ═ CHR (R = Et, ^nPr, ^nBu) in a 1,2-insertion to give the series of THF-free dimeric n-alkyl complexes [Ln(η^5:η^1-C_5Me_4SiMe_2NCMe_3)(μ-CH_2CH_2R)]_2 as isolable crystals. Single-crystal X-ray diffraction studies on the five derivatives [Y(η^5:η^1-C_5Me_4SiMe_2NCMe_2R‘)(μ-CH_2CH_2R)]_2 (R‘ = Me, R = Et, ^nBu; R‘ = Et, R = Et, ^nPr) and [Yb(η^5:η^1-C_5Me_4SiMe_2NCMe_3)(μ-CH_2CH_2^nBu)]_2 revealed that the centrosymmetric dimeric complexes consist of two trans-arranged [Ln(η^5:η^1-C_5Me_4SiMe_2NCMe_2R‘)] fragments connected by two μ-alkyl ligands. Most strikingly, there…
Diene-Containing Half-Sandwich MoIII Complexes as Ethylene Polymerization Catalysts: Experimental and Theoretical Studies
2001
International audience; Seventeen-electron compounds of Mo III having the general formula [(h 5-C 5 R 5)Mo(h 4-diene)X 2 ] (R H, Me; diene butadiene, iso-prene, or 2,3-dimethylbutadiene; X Cl, CH 3) are a new class of ethylene polymerization catalysts. The polyethy-lene obtained shows a bimodal distribution , the major weight fraction being characterized by very long (M around 10 6) and highly linear polymer chains. The newly prepared pentamethylcyclo-pentadienyl (Cp*) derivatives are more active than the cyclopentadienyl (Cp) derivatives, but much less active than previously investigated niobium III compounds having the same stoichiometry. On the other hand, the turnover frequency of the a…
Linked Amido—Cyclopentadienyl Complexes of Group 3 and 4 Metals: The First “Post-Metallocenes”
1999
Linked amido—cyclopentadienyl ligands were introduced by Bercaw and Shapiro in the late eighties with the catalysts of the type Sc(η5:η1-C5Me4SiMe2N t Bu)X (X = H, alkyl) [1]. These electronically more unsaturated and sterically more accessible analogs of ansa-scandocene complexes were found to be capable of catalyzing the living oligomerization of the α-olefins propylene, 1-butene, and 1-pentene. In these complexes the steric constraint [2] of Brintzinger-type ansa-metallocenes is alleviated by the replacement of one cyclopentadienyl ligand by an amido ligand NR’ (Scheme 1). In order to explore sterically demanding derivatives of this dianionic ligand (C5R4ZNR’)2-, iron and titanium comple…
Characterization of β-B-Agostic Isomers in Zirconocene Amidoborane Complexes
2009
The reaction of Cp(x)(2)ZrCl(2) (Cp(x) = Cp, Cp*) with ammonia borane in presence of n-butyllithium yielded Cp(2)Zr(Cl)NH(2)BH(3) and Cp(x)(2)Zr(H)NH(2)BH(3). These derivatives are isoelectronic with the ethyl zirconocene chloride and hydride, respectively, and feature a chelating amidoborane ligand coordinating through a Zr-N bond and a Zr-H-B bridge. In solution, each of the complexes consists of an equilibrium mixture of two isomers differing in the orientation of the amidoborane ligand with respect to the Zr-X bond (X = H, Cl), while in the solid state, only one isomer was observed. Such isomers have not been characterized for any metal complexes containing the isoelectronic beta-agosti…