skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthesis, isolation, and characterization of (K(cryptand 2. 2. 2)) sub 2 (Hf(CO) sub 6 ), the first substance to contain hafnium in a negative oxidation state. Structural characterization of (K(cryptand 2. 2. 2)) sub 2 (M(CO) sub 6 ) times pyridine (M = Ti, Zr, and Hf)

Abstract

Reductive carbonylation of M(CO){sub 4}(CH{sub 3}C(CH{sub 2}PMe{sub 2}){sub 3}), M = Ti, Zr, and Hf, by (K(cryptand 2.2.2))(naphthalene) at {minus}70{degree}C followed by warming provides practically quantitative yields of the thermally robust salts (K(cryptand 2.2.2)){sub 2}(M(CO){sub 6}), including the previously inaccessible (Hf(CO){sub 6}){sup 2{minus}}. X-ray crystal structure analyses show the presence of essentially unperturbed octahedral hexacarbonyl metal units in all three salts. This study represents the first structural characterization of pure carbonylmetallates of the group 4 elements and establishes the existence of a compound containing hafnium in a negative ({minus}2) oxidation state for the first time.

Authors:
;  [1]
  1. Univ. of Minnesota, Minneapolis (USA)
Publication Date:
OSTI Identifier:
6812064
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society; (USA)
Additional Journal Information:
Journal Volume: 112:16; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; HAFNIUM COMPLEXES; CRYSTAL STRUCTURE; SYNTHESIS; DATA ANALYSIS; EXPERIMENTAL DATA; MEASURING INSTRUMENTS; MEASURING METHODS; TITANIUM COMPLEXES; ZIRCONIUM COMPLEXES; COMPLEXES; DATA; INFORMATION; NUMERICAL DATA; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties

Citation Formats

Ellis, J E, and Chi, Kaiming. Synthesis, isolation, and characterization of (K(cryptand 2. 2. 2)) sub 2 (Hf(CO) sub 6 ), the first substance to contain hafnium in a negative oxidation state. Structural characterization of (K(cryptand 2. 2. 2)) sub 2 (M(CO) sub 6 ) times pyridine (M = Ti, Zr, and Hf). United States: N. p., 1990. Web. doi:10.1021/ja00172a017.
Ellis, J E, & Chi, Kaiming. Synthesis, isolation, and characterization of (K(cryptand 2. 2. 2)) sub 2 (Hf(CO) sub 6 ), the first substance to contain hafnium in a negative oxidation state. Structural characterization of (K(cryptand 2. 2. 2)) sub 2 (M(CO) sub 6 ) times pyridine (M = Ti, Zr, and Hf). United States. doi:10.1021/ja00172a017.
Ellis, J E, and Chi, Kaiming. Wed . "Synthesis, isolation, and characterization of (K(cryptand 2. 2. 2)) sub 2 (Hf(CO) sub 6 ), the first substance to contain hafnium in a negative oxidation state. Structural characterization of (K(cryptand 2. 2. 2)) sub 2 (M(CO) sub 6 ) times pyridine (M = Ti, Zr, and Hf)". United States. doi:10.1021/ja00172a017.
@article{osti_6812064,
title = {Synthesis, isolation, and characterization of (K(cryptand 2. 2. 2)) sub 2 (Hf(CO) sub 6 ), the first substance to contain hafnium in a negative oxidation state. Structural characterization of (K(cryptand 2. 2. 2)) sub 2 (M(CO) sub 6 ) times pyridine (M = Ti, Zr, and Hf)},
author = {Ellis, J E and Chi, Kaiming},
abstractNote = {Reductive carbonylation of M(CO){sub 4}(CH{sub 3}C(CH{sub 2}PMe{sub 2}){sub 3}), M = Ti, Zr, and Hf, by (K(cryptand 2.2.2))(naphthalene) at {minus}70{degree}C followed by warming provides practically quantitative yields of the thermally robust salts (K(cryptand 2.2.2)){sub 2}(M(CO){sub 6}), including the previously inaccessible (Hf(CO){sub 6}){sup 2{minus}}. X-ray crystal structure analyses show the presence of essentially unperturbed octahedral hexacarbonyl metal units in all three salts. This study represents the first structural characterization of pure carbonylmetallates of the group 4 elements and establishes the existence of a compound containing hafnium in a negative ({minus}2) oxidation state for the first time.},
doi = {10.1021/ja00172a017},
journal = {Journal of the American Chemical Society; (USA)},
issn = {0002-7863},
number = ,
volume = 112:16,
place = {United States},
year = {1990},
month = {8}
}