PREPARATION AND PROPERTIES OF THE D(O) (ETA(5)-C(5)ME(5))TA(=NR)(2) FUNCTIONAL-GROUP

Citation
Tc. Baldwin et al., PREPARATION AND PROPERTIES OF THE D(O) (ETA(5)-C(5)ME(5))TA(=NR)(2) FUNCTIONAL-GROUP, Inorganic chemistry, 32(25), 1993, pp. 5682-5686
Citations number
42
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
ISSN journal
00201669
Volume
32
Issue
25
Year of publication
1993
Pages
5682 - 5686
Database
ISI
SICI code
0020-1669(1993)32:25<5682:PAPOTD>2.0.ZU;2-H
Abstract
The reaction of 2 equiv of LiNHAr (Ar = 2,6-(C6H3Pr2)-Pr-i) with CpTa Cl4 (Cp = eta(5)-C(5)Me(5)) in THF affords the imido compound Cp*Ta(= NAr)Cl-2 (1). Upon reaction of CpTaCl4 with 4 equiv of LiNHAr in Et(2 )O, the bis(imido) complex [Li(OEt(2))][CpTa(=NAr)Cl] (2) is isolated . The THF adduct [Li(THF)][CpTa(=NAr)(2)Cl] (3) is formed when this r eaction is carried out in THF or when 1 is reacted with 2 equiv of LiN HAr in THF. [Li(OEt(2))][CpTa(=NAr)(2)Cl] (2) crystallizes in the mon oclinic space group P2(1)/n (No. 14) with a = 13.108(3) Angstrom, b = 17.998(5) Angstrom, c = 16.919(4) Angstrom, beta = 96.69(1)degrees, an d V = 3964 (3) Angstrom(3) With Z = 4 and rho(calcd) = 1.31 g cm(-3). The molecular structure of 2 is characterized as containing a mu-[Li(O Et(2))](+) moiety bridging the imide nitrogens. In solution the imido ligands are equivalent with restricted rotation about Ta-N-C-ipso, imp lying an intact [Li(OEt(2))](+) bridge. CpTa(=NAr)(NEt(2))Cl (5; prep ared from Ta(=NAr)(NEt(2))Cl-2(THF)2 (4) and Li[C(5)Me(5)]) reacts wit h LiNHAr (in refluxing THF) to afford [Li(THF)] [CpTa(=NAr)(2)Cl] (3) only very slowly.