Larger and more weakly coordinating anions: Nb(OTeF[sub 5])[sub 6][sup [minus]] and Ti(OTeF[sub 5])[sub 6][sup 2[minus]]

Journal Article · Wed Dec 30 04:00:00 EST 1992 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00053a066· OSTI ID:6348100

Van Seggen, D M; Hurlburt, P K; Anderson, O P; Strauss, S H ^[1]

---

1. Colorado State Univ., Fort Collins (United States)

The ability to generate coordinative unsaturation for a wide variety of cationic species (e.g., [SiR[sub 3]][sup +], [Fe(Por)][sup +], [Re(Cp)(NO)(PPh[sub 3])][sup +], [ZrCp[prime][sub 2]R][sup +]) in solution remains an elusive goal for synthetic and catalytic chemists because no solvent or anion is truly noncoordinating. Recent examples of larger and more weakly coordinating anions include fluorinated derivatives of BPh[sub 4][sup [minus]] such as B(C[sub 6]F[sub 5])[sub 4][sup [minus]] and B(3,5-C[sub 6]H[sub 3](CF[sub 3])[sub 2])[sub 4][sup [minus]6], CB[sub 11]H[sub 12][sup [minus]] and related carborane anions, and heteropolyanions (Keggin ions) such as PW[sub 12]O[sub 40][sup 3[minus]]. The authors are investigating a class of even larger complex anions, M(OTeF[sub 5])[sub 6][sup n[minus]], and have found that they are (i) much less coordinating, (ii) much more stable in the presence of electrophiles, and (iii) much more solubilizing in weakly coordinating solvents than either B(OTeF[sub 5])[sub 4][sup [minus]] or Pd(OTeF[sub 5])[sub 4][sup 2[minus]]. The anions that are the subject of this paper are Nb(OTeF[sub 5])[sub 6][sup [minus]] and Ti(OTeF[sub 5])[sub 6][sup 2[minus]], which had been prepared previously as their TBA[sup +] or Cs[sup +] salts, respectively. The authors have prepared their Ag[sup +] salts, which should prove useful as metathesis reagents, by mixing either NbCl[sub 5] or TiCl[sub 4] with 6 equiv of AgOTeF[sub 5] in 1,1,2-trichlorotrifluoroethane (CFC-113). 22 refs., 1 fig.

• OSTI ID: 6348100
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 114:27; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ANIONS
CHALCOGENIDES
CHARGED PARTICLES
CHEMICAL PREPARATION
CHEMICAL PROPERTIES
COMPLEXES
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
IONS
NIOBIUM COMPLEXES
OXIDES
OXYGEN COMPOUNDS
SALTS
SOLVENTS
SYNTHESIS
TELLURIUM COMPOUNDS
TELLURIUM FLUORIDES
TELLURIUM HALIDES
TELLURIUM OXIDES
TITANIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES