Preparation and properties of the d[sup 0] ((eta)[sup 5] -C[sub 5]Me[sub 5])Ta(=NR)[sub 2] functional group

Journal Article · Wed Dec 08 00:00:00 EST 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00077a006· OSTI ID:5078909

Baldwin, T C; Huber, S R; Bruck, M A; Wigley, D E ^[1]

---

1. Univ. of Arizona, Tucson, AZ (United States)

The reaction of 2 equiv of LiNHAr (Ar = 2,6-C[sub 6]H[sub 3][sup i]Pr[sub 2]) with Cp[sup *]Ta (Cp[sup *] = [eta][sup 5]-C[sub 5]Me[sub 5]) in THF affords the imido compound Cp[sup *]Ta(=NAr)Cl[sub 2] (1). Upon reaction of Cp[sup +]TaCl[sub 4] with 4 equiv of LiNHAr in Et[sub 2]O, the bis(imido) complex [Li(OEt[sub 2])][Cp[sup *]Ta(=NAr)[sub 2]Cl] (2) is isolated. The THF adduct [Li(THF)][Cp[sup *]Ta(=NAr)[sub 2]Cl] (3) is formed when this reaction is carried out in THF or when 1 is reacted with 2 equiv of LiNHAar in THF. [Li-(OEt[sub 2])][Cp[sup 8]Ta(NAr)[sub 2]Cl] (2) crystallizes in the monoclinic space group P2[sub 1]/n (No. 14) with a = 13.108(3)[angstrom], b = 17.998 (5) [angstrom], c =16.919[angstrom], [beta] = 96.69(1)[degrees], and V = 3964 (3) [angstrom] [sup 3] with Z = 4 and [rho][sub calcd] = 1.31 g cm[sup [minus]3]. The molecular structure of 2 is characterized as containing a [mu]-[Li(OEt[sub 2])][sup +] moiety bridging the imide nitrogens. In solution, the imido ligands are equivalent with restricted rotation about Ta-N-C[sub ipso], implying an intact [Li(OEt[sub 2])][sup +] bridge. Cp[sup *]Ta(=NAr)(NEt[sub 2])Cl (5; prepared from Ta(=NAr) (NEt[sub 2])Cl[sub 2](THF)[sub 2] (4) and Li[C[sub 5]Me[sub 5]]) reacts with LiNHAr (in refluxing THF) to afford [Li(THF)][Cp[sup *]Ta(=NAr)[sub 2]Cl] (3) only very slowly.

• OSTI ID: 5078909
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:25; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
TANTALUM COMPLEXES
MOLECULAR STRUCTURE
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
LATTICE PARAMETERS
MONOCLINIC LATTICES
ORGANOMETALLIC COMPOUNDS
COMPLEXES
CRYSTAL LATTICES
ORGANIC COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties