Synthesis and Structure of a New Bulky Hybrid Scorpionate/Cyclopentadienyl Ligand and its Lithium Complex

GND
1298017580
Affiliation
Friedrich Schiller University Jena Institute of Inorganic and Analytical Chemistry Humboldtstraße 8 D-07743 Jena
Mandel, Miles J.;
GND
1214845193
Affiliation
Friedrich Schiller University Jena Institute of Inorganic and Analytical Chemistry Humboldtstraße 8 D-07743 Jena
Görls, Helmar;
GND
1014223741
ORCID
0000-0002-1520-2401
Affiliation
Friedrich Schiller University Jena Institute of Inorganic and Analytical Chemistry Humboldtstraße 8 D-07743 Jena
Westerhausen, Matthias

Abstract The reaction of 5‐(1‐adamantyl)‐3‐methyl‐1 H ‐pyrazole with dibromomethane yields a product mixture of bis(3‐adamantyl‐5‐methylpyrazolyl)methane (H 2 C(Pz Ad,Me ) 2 , 2 a ), (3‐adamantyl‐5‐methylpyrazolyl)‐(3‐methyl‐5‐adamantylpyrazolyl)methane ((H 2 C(Pz Ad,Me )(Pz Me,Ad ), 2 b ) and bis(3‐methyl‐5‐adamantylpyrazolyl)methane (H 2 C(Pz Me,Ad ) 2 , 2 c ). Lithiation of sterically congested H 2 C(Pz Ad,Me ) 2 ( 2 a ) and subsequent addition of diphenylfulvene yields lithium 1,1‐bis(3‐adamantyl‐5‐methylpyrazolyl)‐2,2‐diphenyl‐2‐ethyl‐ cyclo pentadienide, [(thf)Li{Cp−CPh 2 −CHPz Ad,Me }] ( 3 ) which is unable to form a thf adduct but can be hydrolyzed to H 5 C 5 −CPh 2 −CHPz Ad,Me ( 4 ). Adamantyl groups in 5‐position of bis(pyrazolyl)methane, i. e. 2 b and 2 c , prohibit formation of a fulvene adduct. For comparison reasons, [{H 5 C 5 −CPh 2 −CHPz Me2 }LiI] ( 1 b ) has been prepared via protolysis of (thf)lithium 1,1‐bis(3,5‐dimethylpyrazolyl)‐2,2‐diphenyl‐2‐ethyl‐ cyclo pentadienide, [(thf)Li{Cp−CPh 2 −CHPz Me2 }] ( 1 a ), in the presence of calcium iodide.

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