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Synthesis, Structural Characterization, and Reactivity of Group 4 Metallacarboranes Bearing the Ligand [H 2 C(C 5 Me 4 )(C 2 B 9 H 10 )] 3−
Author(s) -
Liu Dongmei,
Shen Hao,
Wang Yaorong,
Cai Yuepeng,
Xie Zuowei
Publication year - 2011
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201000638
Subject(s) - chemistry , tetrahydrofuran , ligand (biochemistry) , amide , reactivity (psychology) , stereochemistry , medicinal chemistry , piperidine , metal , organic chemistry , medicine , biochemistry , receptor , alternative medicine , pathology , solvent
A new organic–inorganic hybrid ligand H 2 C(C 5 Me 4 H)(C 2 B 10 H 11 ) ( 2 ) has been prepared. A selective deboration reaction with piperidine in ethanol resulted in the isolation of [Me 3 NH][H 2 C(C 5 Me 4 H)(C 2 B 9 H 11 )] ( 3 ). An amine‐elimination reaction of 3 with [Zr(NMe 2 ) 4 ] produced a neutral metal‐amide complex [η 5 :η 5 ‐H 2 C(C 5 Me 4 )(C 2 B 9 H 10 )]Zr(NMe 2 )(NHMe 2 ) ( 4 ). The double‐ring‐opening reaction of 4 with tetrahydrofuran (THF) afforded [η 5 :η 5 ‐H 2 C(C 5 Me 4 )(C 2 B 9 H 10 )]Zr (OCH 2 CH 2 CH 2 CH 2 ) 2 N(CH 3 ) 2 ( 5 ). Treatment of the trianionic salt of 3 with [MCl 4 (thf) 2 ] gave complexes [{η 5 :η 5 ‐H 2 C(C 5 Me 4 )(C 2 B 9 H 10 )}M( μ ‐Cl) 2 ][Li(thf) 2 ] (M=Zr ( 6 ), Hf ( 7 )). Reaction of 6 with LiCH 2 TMS generated the ionic species [{η 5 :η 5 ‐H 2 C(C 5 Me 4 )(C 2 B 9 H 10 )}Zr(CH 2 TMS) 2 ][Li(thf) 3 ] ( 9 ). Interaction of complex 6 with KCH 2 (NMe 2 )‐ o ‐C 6 H 4 led to the formation of the neutral metal alkyl complex [η 5 :η 5 ‐H 2 C(C 5 Me 4 )(C 2 B 9 H 10 )]Zr[σ:σ‐CH 2 (NMe 2 )‐ o ‐C 6 H 4 ] ( 10 ). All complexes have been fully characterized by various spectroscopic techniques and elemental analyses. Some were further confirmed by single‐crystal X‐ray analyses.