Addition and metathesis reactions of zirconium and hafnium imido complexes

Joseph L. Thorman; Ilia A. Guzei; Victor G. Young; L. Keith Woo

doi:10.1021/ic9910007

Addition and metathesis reactions of zirconium and hafnium imido complexes

Joseph L. Thorman, Ilia A. Guzei, Victor G. Young, L. Keith Woo

Chemistry (Twin Cities)

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

29 Scopus citations

Abstract

The zirconium and hafnium imido metalloporphyrin complexes (TTP)M=NAr(i(Pr)) (TTP = meso-5,10,15,20-tetra-p-tolylporphyrinato dianion; M = Zr (1), Hf; Ar(i(Pr)) = 2,6-diisopropylphenyl) were used to mediate addition reactions of carbonyl species and metathesis of nitroso compounds. The imido complexes react in a stepwise manner in the presence of 2 equiv of pinacolone to form the enediolate products (TTP)M[OC(¹Bu)CHC(¹Bu)(Me)O] (M = Zr (2), Hf (3)), with elimination of H₂NAr(i(Pr)). The bis(μ-oxo) complex [(TTP)ZrO]₂ (4) is formed upon reaction of (TTP)Zr=NAr(i(Pr)) with PhNO. Treatment of compound 4 with water or treatment of compound 2 with acetone produced the (μ-oxo)bis(μ-hydroxo)-bridged dimer [(TTP)Zr]₂(μ-O)(μ-OH)₂ (5). Compounds 2, 4, and 5 were structurally characterized by single-crystal X-ray diffraction.

Original language	English (US)
Pages (from-to)	2344-2351
Number of pages	8
Journal	Inorganic chemistry
Volume	39
Issue number	11
DOIs	https://doi.org/10.1021/ic9910007
State	Published - May 29 2000

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title = "Addition and metathesis reactions of zirconium and hafnium imido complexes",

abstract = "The zirconium and hafnium imido metalloporphyrin complexes (TTP)M=NAr(i(Pr)) (TTP = meso-5,10,15,20-tetra-p-tolylporphyrinato dianion; M = Zr (1), Hf; Ar(i(Pr)) = 2,6-diisopropylphenyl) were used to mediate addition reactions of carbonyl species and metathesis of nitroso compounds. The imido complexes react in a stepwise manner in the presence of 2 equiv of pinacolone to form the enediolate products (TTP)M[OC(1Bu)CHC(1Bu)(Me)O] (M = Zr (2), Hf (3)), with elimination of H2NAr(i(Pr)). The bis(μ-oxo) complex [(TTP)ZrO]2 (4) is formed upon reaction of (TTP)Zr=NAr(i(Pr)) with PhNO. Treatment of compound 4 with water or treatment of compound 2 with acetone produced the (μ-oxo)bis(μ-hydroxo)-bridged dimer [(TTP)Zr]2(μ-O)(μ-OH)2 (5). Compounds 2, 4, and 5 were structurally characterized by single-crystal X-ray diffraction.",

author = "Thorman, {Joseph L.} and Guzei, {Ilia A.} and Young, {Victor G.} and Woo, {L. Keith}",

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AU - Thorman, Joseph L.

AU - Guzei, Ilia A.

AU - Young, Victor G.

AU - Woo, L. Keith

PY - 2000/5/29

Y1 - 2000/5/29

N2 - The zirconium and hafnium imido metalloporphyrin complexes (TTP)M=NAr(i(Pr)) (TTP = meso-5,10,15,20-tetra-p-tolylporphyrinato dianion; M = Zr (1), Hf; Ar(i(Pr)) = 2,6-diisopropylphenyl) were used to mediate addition reactions of carbonyl species and metathesis of nitroso compounds. The imido complexes react in a stepwise manner in the presence of 2 equiv of pinacolone to form the enediolate products (TTP)M[OC(1Bu)CHC(1Bu)(Me)O] (M = Zr (2), Hf (3)), with elimination of H2NAr(i(Pr)). The bis(μ-oxo) complex [(TTP)ZrO]2 (4) is formed upon reaction of (TTP)Zr=NAr(i(Pr)) with PhNO. Treatment of compound 4 with water or treatment of compound 2 with acetone produced the (μ-oxo)bis(μ-hydroxo)-bridged dimer [(TTP)Zr]2(μ-O)(μ-OH)2 (5). Compounds 2, 4, and 5 were structurally characterized by single-crystal X-ray diffraction.

AB - The zirconium and hafnium imido metalloporphyrin complexes (TTP)M=NAr(i(Pr)) (TTP = meso-5,10,15,20-tetra-p-tolylporphyrinato dianion; M = Zr (1), Hf; Ar(i(Pr)) = 2,6-diisopropylphenyl) were used to mediate addition reactions of carbonyl species and metathesis of nitroso compounds. The imido complexes react in a stepwise manner in the presence of 2 equiv of pinacolone to form the enediolate products (TTP)M[OC(1Bu)CHC(1Bu)(Me)O] (M = Zr (2), Hf (3)), with elimination of H2NAr(i(Pr)). The bis(μ-oxo) complex [(TTP)ZrO]2 (4) is formed upon reaction of (TTP)Zr=NAr(i(Pr)) with PhNO. Treatment of compound 4 with water or treatment of compound 2 with acetone produced the (μ-oxo)bis(μ-hydroxo)-bridged dimer [(TTP)Zr]2(μ-O)(μ-OH)2 (5). Compounds 2, 4, and 5 were structurally characterized by single-crystal X-ray diffraction.

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Addition and metathesis reactions of zirconium and hafnium imido complexes

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