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Title: Highly reduced organometallics. 20. The first general synthetic route to zerovalent titanium carbonyls. Synthesis and properties of Ti(CO)/sub 5/(Me/sub 2/PCH/sub 2/CH/sub 2/PMe/sub 2/)

Abstract

Synthetic procedures developed in this study provide the first general route to zerovalent titanium carbonyls and should facilitate future investigations in this relatively unexplored area of organotitanium chemistry. Sodium naphthalenide reductions of TiCL/sub 4/(THF)/sub 2/ (THF = tetrahydrofuran), in the presence of 2.1-2.3 equiv of Me/sub 2/PCH/sub 2/CH/sub 2/PMe/sub 2/ (dmpe) in THF at -70 to -80/sup 0/ under argon, followed by carbonylation at atmospheric pressure provide 70-80% isolated yields of the previously known but relatively inaccessible Ti(CO)/sub 3/(dmpe)/sub 2/. Under a carbon monoxide atmosphere at room temperature within 3 h, the latter is partially converted to Ti(CO)/sub 5/(dmpe), the initial example of a pentacarbonyltitanium species. Addition of about 2 equiv of BH/sub 3/ x THF to the Ti(CO)/sub 3/(dmpe)/sub 2//Ti(CO)/sub 5/(dmpe) mixture under a CO atmosphere in THF binds free dmpe as dmpe x 2BH/sub 3/ and causes disappearance of all Ti(CO)/sub 3/(dmpe)/sub 2/, thereby allowing the isolation of substantially pure Ti(CO)/sub 5/(dmpe). The latter is a bright red crystalline material that decomposes within hours at room temperature and has been characterized by infrared, /sup 13/C, /sup 31/P, and /sup 1/H NMR spectroscopy. Unlike Ti(CO)/sub 3/(dmpe)/sub 2/, the pentacarbonyl compound is quite reactive toward a variety of main groupmore » nucleophiles and thereby represents the first accessible synthetic equivalent of the unknown Ti(CO)/sub 7/. Its reactions with 1,1,1-tris(dimethylphosphinomethyl)ethane (trmpe), sodium cyclopentadienide, sodium indenide, and potassium hydrotris(1-pyrazolyl)borate ((HB(Pz)/sub 3/)Ti(CO)/sub 4//sup -/.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis (USA)
OSTI Identifier:
7247306
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.; (United States)
Additional Journal Information:
Journal Volume: 110:1
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBONYLS; CHEMICAL PREPARATION; CHEMICAL PROPERTIES; ORGANOMETALLIC COMPOUNDS; TITANIUM COMPOUNDS; CHEMICAL REACTION YIELD; EXPERIMENTAL DATA; DATA; INFORMATION; NUMERICAL DATA; ORGANIC COMPOUNDS; SYNTHESIS; TRANSITION ELEMENT COMPOUNDS; YIELDS; 400201* - Chemical & Physicochemical Properties

Citation Formats

Chi, K M, Frerichs, S R, Stein, B K, Blackburn, D W, and Ellis, J E. Highly reduced organometallics. 20. The first general synthetic route to zerovalent titanium carbonyls. Synthesis and properties of Ti(CO)/sub 5/(Me/sub 2/PCH/sub 2/CH/sub 2/PMe/sub 2/). United States: N. p., 1988. Web. doi:10.1021/ja00209a026.
Chi, K M, Frerichs, S R, Stein, B K, Blackburn, D W, & Ellis, J E. Highly reduced organometallics. 20. The first general synthetic route to zerovalent titanium carbonyls. Synthesis and properties of Ti(CO)/sub 5/(Me/sub 2/PCH/sub 2/CH/sub 2/PMe/sub 2/). United States. https://doi.org/10.1021/ja00209a026
Chi, K M, Frerichs, S R, Stein, B K, Blackburn, D W, and Ellis, J E. 1988. "Highly reduced organometallics. 20. The first general synthetic route to zerovalent titanium carbonyls. Synthesis and properties of Ti(CO)/sub 5/(Me/sub 2/PCH/sub 2/CH/sub 2/PMe/sub 2/)". United States. https://doi.org/10.1021/ja00209a026.
@article{osti_7247306,
title = {Highly reduced organometallics. 20. The first general synthetic route to zerovalent titanium carbonyls. Synthesis and properties of Ti(CO)/sub 5/(Me/sub 2/PCH/sub 2/CH/sub 2/PMe/sub 2/)},
author = {Chi, K M and Frerichs, S R and Stein, B K and Blackburn, D W and Ellis, J E},
abstractNote = {Synthetic procedures developed in this study provide the first general route to zerovalent titanium carbonyls and should facilitate future investigations in this relatively unexplored area of organotitanium chemistry. Sodium naphthalenide reductions of TiCL/sub 4/(THF)/sub 2/ (THF = tetrahydrofuran), in the presence of 2.1-2.3 equiv of Me/sub 2/PCH/sub 2/CH/sub 2/PMe/sub 2/ (dmpe) in THF at -70 to -80/sup 0/ under argon, followed by carbonylation at atmospheric pressure provide 70-80% isolated yields of the previously known but relatively inaccessible Ti(CO)/sub 3/(dmpe)/sub 2/. Under a carbon monoxide atmosphere at room temperature within 3 h, the latter is partially converted to Ti(CO)/sub 5/(dmpe), the initial example of a pentacarbonyltitanium species. Addition of about 2 equiv of BH/sub 3/ x THF to the Ti(CO)/sub 3/(dmpe)/sub 2//Ti(CO)/sub 5/(dmpe) mixture under a CO atmosphere in THF binds free dmpe as dmpe x 2BH/sub 3/ and causes disappearance of all Ti(CO)/sub 3/(dmpe)/sub 2/, thereby allowing the isolation of substantially pure Ti(CO)/sub 5/(dmpe). The latter is a bright red crystalline material that decomposes within hours at room temperature and has been characterized by infrared, /sup 13/C, /sup 31/P, and /sup 1/H NMR spectroscopy. Unlike Ti(CO)/sub 3/(dmpe)/sub 2/, the pentacarbonyl compound is quite reactive toward a variety of main group nucleophiles and thereby represents the first accessible synthetic equivalent of the unknown Ti(CO)/sub 7/. Its reactions with 1,1,1-tris(dimethylphosphinomethyl)ethane (trmpe), sodium cyclopentadienide, sodium indenide, and potassium hydrotris(1-pyrazolyl)borate ((HB(Pz)/sub 3/)Ti(CO)/sub 4//sup -/.},
doi = {10.1021/ja00209a026},
url = {https://www.osti.gov/biblio/7247306}, journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 110:1,
place = {United States},
year = {Wed Jan 06 00:00:00 EST 1988},
month = {Wed Jan 06 00:00:00 EST 1988}
}