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Title: Metal alkoxides - models for metal oxides. 1. Preparations and structures of hexadecaalkoxytetatungsten compounds, W/sub 4/(OR)/sub 16/, where R = Me and Et, and octaoxotetraisopropoxytetrapyridinotetramolybdenum, Mo/sub 4/(O)/sub 4/(. mu. -O)/sub 2/(. mu. /sub 3/-O)/sub 2/(O-i-Pr)/sub 2/(. mu. -O-i-Pr)/sub 2/(py)/sub 4/

Abstract

In hydrocarbon solvents, W/sub 2/(NMe/sub 2/)/sub 6/ (M = M) and each of the alcohols, MeOH and EtOH, react to give tetranuclar compounds, W/sub 4/(OR/sub 16/ (R = Me and Et), by alcoholysis and oxidation of tungsten, 3+ to 4+. These new compounds have been characterized by a variety of physicochemical techniques including, for the ethoxide, a single-crystal x-ray diffraction study. By the formation of alkoxy bridges, each tungsten atom attains an octahedral coordination. The M/sub 4/O/sub 16/ skeleton is akin to those found in the anion W/sub 4/O/sub 16//sup 8 -/ and the neutral alkoxide (Ti(OEt)/sub 4/)/sub 4/, but the eight electrons associated with the four W(4+)d/sup 2/ atoms lead to cluster-W/sub 4/ bonding as evidenced by a comparison of M-M distances. From the reaction between Mo/sub 2/(O-i-Pr)/sub 6/ (M = M) and molecular oxygen in pyridine, a minor product, formed in ca. 15% yield based on Mo, is shown to be Mo/sub 4/O/sub 8/(O-i-Pr)/sub 4/(py)/sub 4/ by a complete x-ray diffraction study. The central Mo/sub 4/O/sub 8/O/sub 4/N/sub 4/ moiety is closely related to those mentioned above. The average oxidation state of molybdenum is +5, and the four electrons available for M-M bonding form two localized M-M singlemore » bonds. These observations lead us to propose that (1) metal alkoxides provide hydrocarbon-soluble models for metal oxides and (2) there should be a large class of structurally related M/sub 4/X/sub a/Y/sub b/Z/sub c/ cluster compounds (a + b + c = 16) in which the metal atoms achieve an octahedral environment and by appropriate variations of ligands and metals, have 0 through 12 electrons for M-M bonding. Crystal data are presented for W/sub 4/(OEt)/sub 16/.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Indiana Univ., Bloomington
OSTI Identifier:
5690026
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.; (United States)
Additional Journal Information:
Journal Volume: 103:20
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MOLYBDENUM COMPOUNDS; CRYSTAL STRUCTURE; ORGANOMETALLIC COMPOUNDS; TUNGSTEN COMPOUNDS; BOND ANGLE; BOND LENGTHS; ETHANOL; EXPERIMENTAL DATA; METHANOL; PYRIDINIUM COMPOUNDS; X-RAY DIFFRACTION; ALCOHOLS; AMINES; AMMONIUM COMPOUNDS; AZINES; COHERENT SCATTERING; DATA; DIFFRACTION; DIMENSIONS; HETEROCYCLIC COMPOUNDS; HYDROXY COMPOUNDS; INFORMATION; LENGTH; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; PYRIDINES; QUATERNARY COMPOUNDS; SCATTERING; TRANSITION ELEMENT COMPOUNDS; 400201* - Chemical & Physicochemical Properties; 400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)

Citation Formats

Chisholm, M H, Huffman, J C, Kirkpatrick, C C, Leonelli, J, and Folting, K. Metal alkoxides - models for metal oxides. 1. Preparations and structures of hexadecaalkoxytetatungsten compounds, W/sub 4/(OR)/sub 16/, where R = Me and Et, and octaoxotetraisopropoxytetrapyridinotetramolybdenum, Mo/sub 4/(O)/sub 4/(. mu. -O)/sub 2/(. mu. /sub 3/-O)/sub 2/(O-i-Pr)/sub 2/(. mu. -O-i-Pr)/sub 2/(py)/sub 4/. United States: N. p., 1981. Web. doi:10.1021/ja00410a018.
Chisholm, M H, Huffman, J C, Kirkpatrick, C C, Leonelli, J, & Folting, K. Metal alkoxides - models for metal oxides. 1. Preparations and structures of hexadecaalkoxytetatungsten compounds, W/sub 4/(OR)/sub 16/, where R = Me and Et, and octaoxotetraisopropoxytetrapyridinotetramolybdenum, Mo/sub 4/(O)/sub 4/(. mu. -O)/sub 2/(. mu. /sub 3/-O)/sub 2/(O-i-Pr)/sub 2/(. mu. -O-i-Pr)/sub 2/(py)/sub 4/. United States. doi:10.1021/ja00410a018.
Chisholm, M H, Huffman, J C, Kirkpatrick, C C, Leonelli, J, and Folting, K. Wed . "Metal alkoxides - models for metal oxides. 1. Preparations and structures of hexadecaalkoxytetatungsten compounds, W/sub 4/(OR)/sub 16/, where R = Me and Et, and octaoxotetraisopropoxytetrapyridinotetramolybdenum, Mo/sub 4/(O)/sub 4/(. mu. -O)/sub 2/(. mu. /sub 3/-O)/sub 2/(O-i-Pr)/sub 2/(. mu. -O-i-Pr)/sub 2/(py)/sub 4/". United States. doi:10.1021/ja00410a018.
@article{osti_5690026,
title = {Metal alkoxides - models for metal oxides. 1. Preparations and structures of hexadecaalkoxytetatungsten compounds, W/sub 4/(OR)/sub 16/, where R = Me and Et, and octaoxotetraisopropoxytetrapyridinotetramolybdenum, Mo/sub 4/(O)/sub 4/(. mu. -O)/sub 2/(. mu. /sub 3/-O)/sub 2/(O-i-Pr)/sub 2/(. mu. -O-i-Pr)/sub 2/(py)/sub 4/},
author = {Chisholm, M H and Huffman, J C and Kirkpatrick, C C and Leonelli, J and Folting, K},
abstractNote = {In hydrocarbon solvents, W/sub 2/(NMe/sub 2/)/sub 6/ (M = M) and each of the alcohols, MeOH and EtOH, react to give tetranuclar compounds, W/sub 4/(OR/sub 16/ (R = Me and Et), by alcoholysis and oxidation of tungsten, 3+ to 4+. These new compounds have been characterized by a variety of physicochemical techniques including, for the ethoxide, a single-crystal x-ray diffraction study. By the formation of alkoxy bridges, each tungsten atom attains an octahedral coordination. The M/sub 4/O/sub 16/ skeleton is akin to those found in the anion W/sub 4/O/sub 16//sup 8 -/ and the neutral alkoxide (Ti(OEt)/sub 4/)/sub 4/, but the eight electrons associated with the four W(4+)d/sup 2/ atoms lead to cluster-W/sub 4/ bonding as evidenced by a comparison of M-M distances. From the reaction between Mo/sub 2/(O-i-Pr)/sub 6/ (M = M) and molecular oxygen in pyridine, a minor product, formed in ca. 15% yield based on Mo, is shown to be Mo/sub 4/O/sub 8/(O-i-Pr)/sub 4/(py)/sub 4/ by a complete x-ray diffraction study. The central Mo/sub 4/O/sub 8/O/sub 4/N/sub 4/ moiety is closely related to those mentioned above. The average oxidation state of molybdenum is +5, and the four electrons available for M-M bonding form two localized M-M single bonds. These observations lead us to propose that (1) metal alkoxides provide hydrocarbon-soluble models for metal oxides and (2) there should be a large class of structurally related M/sub 4/X/sub a/Y/sub b/Z/sub c/ cluster compounds (a + b + c = 16) in which the metal atoms achieve an octahedral environment and by appropriate variations of ligands and metals, have 0 through 12 electrons for M-M bonding. Crystal data are presented for W/sub 4/(OEt)/sub 16/.},
doi = {10.1021/ja00410a018},
journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 103:20,
place = {United States},
year = {1981},
month = {10}
}