Synthesis and isocyanate insertion reactions of tungsten(IV) imido complexes formed from W(CO)(acac)(N3)(PMe3)3 with azide as the oxidant

Chetna Khosla; Andrew B. Jackson; Peter S. White; Joseph L. Templeton

doi:10.1016/j.ica.2010.10.032

Synthesis and isocyanate insertion reactions of tungsten(IV) imido complexes formed from W(CO)(acac)(N₃)(PMe₃)₃ with azide as the oxidant

Chetna Khosla, Andrew B. Jackson, Peter S. White, Joseph L. Templeton

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

Abstract

Addition of excess trimethylphosphine and a halide source to a solution of W(CO)(acac)₂(η²-L) (L = NCPh and OCMe₂) leads to displacement of L and one acetylacetonate chelate to produce electron-rich, seven-coordinate complexes of the formula W(CO)(acac)(X)(PMe ₃)₃ (X = Cl, Br, and I). Use of NaN₃ instead of a halide source leads primarily to loss of carbon monoxide and dinitrogen, and protonation from adventitious water yields the cationic imido complex [W(NH)(acac)(PMe₃)₃]⁺. Heating [W(NH)(acac)(PMe₃)₃]⁺ in aromatic isocyanates at high temperature results in isocyanate insertion into the NH imido bond to form new C-N bonds. An alternate route to related imido complexes involves heating [W(O)(acac)(PMe₃)₃]⁺ with phenyl isocyanate at high temperatures to yield the substituted imido complex [W(NPh)(acac)(PMe₃)₃]⁺.

Original language	English (US)
Pages (from-to)	19-31
Number of pages	13
Journal	Inorganica Chimica Acta
Volume	369
Issue number	1
DOIs	https://doi.org/10.1016/j.ica.2010.10.032
State	Published - Apr 15 2011
Externally published	Yes

Keywords

Insertion chemistry
Organometallic synthesis
Tungsten imido chemistry
X-ray crystal structure

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.ica.2010.10.032

Cite this

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title = "Synthesis and isocyanate insertion reactions of tungsten(IV) imido complexes formed from W(CO)(acac)(N3)(PMe3)3 with azide as the oxidant",

abstract = "Addition of excess trimethylphosphine and a halide source to a solution of W(CO)(acac)2(η2-L) (L = NCPh and OCMe2) leads to displacement of L and one acetylacetonate chelate to produce electron-rich, seven-coordinate complexes of the formula W(CO)(acac)(X)(PMe 3)3 (X = Cl, Br, and I). Use of NaN3 instead of a halide source leads primarily to loss of carbon monoxide and dinitrogen, and protonation from adventitious water yields the cationic imido complex [W(NH)(acac)(PMe3)3]+. Heating [W(NH)(acac)(PMe3)3]+ in aromatic isocyanates at high temperature results in isocyanate insertion into the NH imido bond to form new C-N bonds. An alternate route to related imido complexes involves heating [W(O)(acac)(PMe3)3]+ with phenyl isocyanate at high temperatures to yield the substituted imido complex [W(NPh)(acac)(PMe3)3]+.",

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AU - Khosla, Chetna

AU - Jackson, Andrew B.

AU - White, Peter S.

AU - Templeton, Joseph L.

PY - 2011/4/15

Y1 - 2011/4/15

N2 - Addition of excess trimethylphosphine and a halide source to a solution of W(CO)(acac)2(η2-L) (L = NCPh and OCMe2) leads to displacement of L and one acetylacetonate chelate to produce electron-rich, seven-coordinate complexes of the formula W(CO)(acac)(X)(PMe 3)3 (X = Cl, Br, and I). Use of NaN3 instead of a halide source leads primarily to loss of carbon monoxide and dinitrogen, and protonation from adventitious water yields the cationic imido complex [W(NH)(acac)(PMe3)3]+. Heating [W(NH)(acac)(PMe3)3]+ in aromatic isocyanates at high temperature results in isocyanate insertion into the NH imido bond to form new C-N bonds. An alternate route to related imido complexes involves heating [W(O)(acac)(PMe3)3]+ with phenyl isocyanate at high temperatures to yield the substituted imido complex [W(NPh)(acac)(PMe3)3]+.

AB - Addition of excess trimethylphosphine and a halide source to a solution of W(CO)(acac)2(η2-L) (L = NCPh and OCMe2) leads to displacement of L and one acetylacetonate chelate to produce electron-rich, seven-coordinate complexes of the formula W(CO)(acac)(X)(PMe 3)3 (X = Cl, Br, and I). Use of NaN3 instead of a halide source leads primarily to loss of carbon monoxide and dinitrogen, and protonation from adventitious water yields the cationic imido complex [W(NH)(acac)(PMe3)3]+. Heating [W(NH)(acac)(PMe3)3]+ in aromatic isocyanates at high temperature results in isocyanate insertion into the NH imido bond to form new C-N bonds. An alternate route to related imido complexes involves heating [W(O)(acac)(PMe3)3]+ with phenyl isocyanate at high temperatures to yield the substituted imido complex [W(NPh)(acac)(PMe3)3]+.

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KW - Tungsten imido chemistry

KW - X-ray crystal structure

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