Methylidenkomplexe der Seltenerdmetalle

The reaction of monomeric [(Tp(tBu,Me) )LuMe2 ] (Tp(tBu,Me) =tris(3-Me-5-tBu-pyrazolyl)borate) with primary aliphatic amines H2 NR (R=tBu, Ad=adamantyl) led to lutetium methyl primary amide complexes [(Tp(tBu,Me) )LuMe(NHR)], the solid-state structures of which were determined by XRD analyses. The mixed methyl/tetramethylaluminate compounds [(Tp(tBu,Me) )LnMe({μ2 -Me}AlMe3 )] (Ln=Y, Ho) reacted selectively and in high yield with H2 NR, according to methane elimination, to afford heterobimetallic complexes: [(Tp(tBu,Me) )Ln({μ2 -Me}AlMe2 )(μ2 -NR)] (Ln=Y, Ho). X-ray structure analyses revealed that the monomeric alkylaluminum-supported imide complexes were isostructural, featuring bridging methyl and imido ligands. Deeper insight into the fluxional behavior in solution was gained by (1) H and (13) C NMR spectroscopic studies at variable temperatures and (1) H-(89) Y HSQC NMR spectroscopy. Treatment of [(Tp(tBu,Me) )LnMe(AlMe4 )] with H2 NtBu gave dimethyl compounds [(Tp(tBu,Me) )LnMe2 ] as minor side products for the mid-sized metals yttrium and holmium and in high yield for the smaller lutetium. Preparative-scale amounts of complexes [(Tp(tBu,Me) )LnMe2 ] (Ln=Y, Ho, Lu) were made accessible through aluminate cleavage of [(Tp(tBu,Me) )LnMe(AlMe4 )] with N,N,N',N'-tetramethylethylenediamine (tmeda). The solid-state structures of [(Tp(tBu,Me) )HoMe(AlMe4 )] and [(Tp(tBu,Me) )HoMe2 ] were analyzed by XRD.

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Rare‐Earth‐Metal Methyl, Amide, and Imide Complexes Supported by a Superbulky Scorpionate Ligand

Schädle

Maichle‐Mößmer

Schädle

et al. 2014

Chemistry A European J

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Lutetium‐Methanediide‐Alkyl Complexes: Synthesis and Chemistry

Wang

Liu

et al. 2014

Chemistry A European J

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The first four-coordinate methanediide/alkyl lutetium complex (BODDI)Lu2 (CH2 SiMe3 )2 (μ2 -CHSiMe3 )(THF)2 (BODDI=ArNC(Me)CHCOCHC(Me)NAr, Ar=2,6-iPr2 C6 H3 ) (1) was synthesized by a thermolysis methodology through α-H abstraction from a Lu-CH2 SiMe3 group. Complex 1 reacted with equimolar 2,6-iPrC6 H3 NH2 and Ph2 C+O to give the corresponding lutetium bridging imido and oxo complexes (BODDI)Lu2 (CH2 SiMe3 )2 (μ2 -N-2,6-iPr2 C6 H3 )(THF)2 (2) and (BODDI)Lu2 (CH2 SiMe3 )2 (μ2 -O)(THF)2 (3). Treatment of 3 with Ph2 C=O (4 equiv) caused a rare insertion of Lu-μ2 -O bond into theC=O group to afford a diphenylmethyl diolate complex 4. Reaction of 1 with PhN=C=O (2 equiv) led to the migration of SiMe3 to the amido nitrogen atom to give complex (BODDI)Lu2 (CH2 SiMe3 )2 -μ-{PhNC(O)CHC(O)NPh(SiMe3 )-κ(3) N,O,O}(THF) (5). Reaction of 1 withtBuN=C formed an unprecedented product (BODDI)Lu2 (CH2 SiMe3 ){μ2 -[η(2) :η(2) -tBuN=C(=CH2 )SiMe2 CHC=NtBu-κ(1) N]}(tBuN=C)2 (6) through a cascade reaction of N=C bond insertion, sequential cyclometalative γ-(sp(3) )-H activation, C=C bond formation, and rearrangement of the newly formed carbene intermediate. The possible mechanistic pathways between 1, PhN=C=O, and tBuN=C were elucidated by DFT calculations.

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Non‐Pincer‐Type Mononuclear Scandium Alkylidene Complexes: Synthesis, Bonding, and Reactivity

Wang

Zhou

Zhao

et al. 2015

Chemistry A European J

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The first non-pincer-type mononuclear scandium alkylidene complexes were synthesized and structurally characterized. These complexes exhibited short Sc-C bond lengths and even one of the shortest reported to date (2.1134(18) Å). The multiple character of the Sc-C bond was highlighted by a DFT calculation. This was confirmed by experimental reactivity study where the complex underwent [2+1] cycloaddition with elemental selenium and [2+2] cycloaddition with imine. DFT calculation also revealed a strong nucleophilic behavior of the alkylidene complex that was experimentally demonstrated by the C-H bond activation of phenylacetylene.

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Methylidenkomplexe der Seltenerdmetalle

Cited by 8 publications

References 50 publications

Rare‐Earth‐Metal Methyl, Amide, and Imide Complexes Supported by a Superbulky Scorpionate Ligand

Rare‐Earth‐Metal Methyl, Amide, and Imide Complexes Supported by a Superbulky Scorpionate Ligand

Lutetium‐Methanediide‐Alkyl Complexes: Synthesis and Chemistry

Non‐Pincer‐Type Mononuclear Scandium Alkylidene Complexes: Synthesis, Bonding, and Reactivity

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