Chemistry of Oxophilic Transition Metals. 4. Reactivity of the Organozirconium(III) Complex (μ-η5:η5-C10H8)[(μ-Cl)Zr(η5-C5H5)]2 with Diphenyldiazomethane, tert-Butyl Isocyanide, and Trimethylsilyl Azide: Diazo, Cyano, and Imido Complexes

Wolfgang A. Herrmann; Babilin Menj; Eberhardt Herdtweck

doi:10.1021/om00053a015

Chemistry of Oxophilic Transition Metals. 4. Reactivity of the Organozirconium(III) Complex (μ-η⁵:η⁵-C₁₀H₈)[(μ-Cl)Zr(η⁵-C₅H₅)]₂ with Diphenyldiazomethane, tert-Butyl Isocyanide, and Trimethylsilyl Azide: Diazo, Cyano, and Imido Complexes

Wolfgang A. Herrmann
, Babilin Menj
, Eberhardt Herdtweck

Technical University of Munich

Technical University of Munich

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

37 Scopus citations

Abstract

The fulvalene zirconium(III) complex (μ-η⁵:η⁵-C₁₀H₈)[(μ-Cl)Zr(η⁵-C₅H₅)]₂ (1) reacts with stoichiometric amounts of diphenyldiazomethane, N₂=C(C₆H5)₂, and with tert-butyl isocyanide, C≡NC(CH₃)₃, to give the 1:1 addition products [μ-η¹:η²-N₂(C₆H₅)₂](μ-η⁵:η⁵-C₁₀H₈)[(η⁵-C₅H₅)ZrCl]₂ (3) and [μ-η¹:η²-CNC-(CH₃)₃](μ-η⁵:η⁵-C₁₀H₈)[(η⁵-C₅H₅)ZrCl]₂ (4), respectively. On the other hand, the reaction of 1 with trimethylsilyl azide, (CH₃)₃SiN₃, takes place under loss of molecular nitrogen, yielding a mixture of (μ-η⁵:η⁵-C₁₀H₈)[(η⁵-C₅H₅)ZrCl₂]₂ (5) and (μ-η⁵:η⁵-C₁₀H₈)(μ-NSUCH₃)₃Zr(η⁵-C₅H₅)]₂ (6). The crystal and molecular structures of 3 and 4 have been determined by X-ray diffraction methods. 3 crystallizes in a triclinic unit cell of PI symmetry with a = 9.189 (1) Å, b = 10.808 (1) Å, c = 15.833 (1) Å, α = 104.93 (1)°, ß = 100.35 (1)°, γ = 97.82 (1)°, V = 1467 Å³, Z = 2, and d_calc = 1.598 g cm⁻³. 4 crystallizes in an orthorhombic crystal lattice of P2₁2₁2₁ symmetry with a = 8.233 (1) Å, b = 16.891 (2) Å, c = 17.312 (2) Å, V = 2407 Å³, Z = 4, and d_calc = 1.641 g cm⁻³. Both structures can be regarded as a result of diphenyldiazomethane and tert-butyl isocyanide insertion into the Zr-Zr bond of 1 with concomitant splitting (opening) of the chloride bridges. The unsaturated organic molecule acts as a bridging ligand, coordinated in a (σ + π) fashion. Sodium amalgam reduction of 4 in the presence of C≡NC(CH₃)₃ unexpectedly yields the cyano complex (μ-η⁵:η⁵-C₁₀H₈)[(μ-η¹:η²-CN)(η⁵-C₅H₅)]₂ (8), whose structure has been inferred from IR and ¹H and ¹³C NMR spectroscopic data.

Original language	English
Pages (from-to)	2134-2141
Number of pages	8
Journal	Organometallics
Volume	10
Issue number	7
DOIs	https://doi.org/10.1021/om00053a015
State	Published - 1 Jul 1991

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@article{ea8ef64b8fc54fddbb87e86e4c81e9a2,

title = "Chemistry of Oxophilic Transition Metals. 4. Reactivity of the Organozirconium(III) Complex (μ-η5:η5-C10H8)[(μ-Cl)Zr(η5-C5H5)]2 with Diphenyldiazomethane, tert-Butyl Isocyanide, and Trimethylsilyl Azide: Diazo, Cyano, and Imido Complexes",

abstract = "The fulvalene zirconium(III) complex (μ-η5:η5-C10H8)[(μ-Cl)Zr(η5-C5H5)]2 (1) reacts with stoichiometric amounts of diphenyldiazomethane, N2=C(C6H5)2, and with tert-butyl isocyanide, C≡NC(CH3)3, to give the 1:1 addition products [μ-η1:η2-N2(C6H5)2](μ-η5:η5-C10H8)[(η5-C5H5)ZrCl]2 (3) and [μ-η1:η2-CNC-(CH3)3](μ-η5:η5-C10H8)[(η5-C5H5)ZrCl]2 (4), respectively. On the other hand, the reaction of 1 with trimethylsilyl azide, (CH3)3SiN3, takes place under loss of molecular nitrogen, yielding a mixture of (μ-η5:η5-C10H8)[(η5-C5H5)ZrCl2]2 (5) and (μ-η5:η5-C10H8)(μ-NSUCH3)3Zr(η5-C5H5)]2 (6). The crystal and molecular structures of 3 and 4 have been determined by X-ray diffraction methods. 3 crystallizes in a triclinic unit cell of PI symmetry with a = 9.189 (1) {\AA}, b = 10.808 (1) {\AA}, c = 15.833 (1) {\AA}, α = 104.93 (1)°, {\ss} = 100.35 (1)°, γ = 97.82 (1)°, V = 1467 {\AA}3, Z = 2, and dcalc = 1.598 g cm−3. 4 crystallizes in an orthorhombic crystal lattice of P212121 symmetry with a = 8.233 (1) {\AA}, b = 16.891 (2) {\AA}, c = 17.312 (2) {\AA}, V = 2407 {\AA}3, Z = 4, and dcalc = 1.641 g cm−3. Both structures can be regarded as a result of diphenyldiazomethane and tert-butyl isocyanide insertion into the Zr-Zr bond of 1 with concomitant splitting (opening) of the chloride bridges. The unsaturated organic molecule acts as a bridging ligand, coordinated in a (σ + π) fashion. Sodium amalgam reduction of 4 in the presence of C≡NC(CH3)3 unexpectedly yields the cyano complex (μ-η5:η5-C10H8)[(μ-η1:η2-CN)(η5-C5H5)]2 (8), whose structure has been inferred from IR and 1H and 13C NMR spectroscopic data.",

author = "Herrmann, \{Wolfgang A.\} and Babilin Menj and Eberhardt Herdtweck",

year = "1991",

month = jul,

day = "1",

doi = "10.1021/om00053a015",

language = "English",

volume = "10",

pages = "2134--2141",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "7",

}

Herrmann, WA, Menj, B & Herdtweck, E 1991, 'Chemistry of Oxophilic Transition Metals. 4. Reactivity of the Organozirconium(III) Complex (μ-η⁵:η⁵-C₁₀H₈)[(μ-Cl)Zr(η⁵-C₅H₅)]₂ with Diphenyldiazomethane, tert-Butyl Isocyanide, and Trimethylsilyl Azide: Diazo, Cyano, and Imido Complexes', Organometallics, vol. 10, no. 7, pp. 2134-2141. https://doi.org/10.1021/om00053a015

Chemistry of Oxophilic Transition Metals. 4. Reactivity of the Organozirconium(III) Complex (μ-η⁵:η⁵-C₁₀H₈)[(μ-Cl)Zr(η⁵-C₅H₅)]₂ with Diphenyldiazomethane, tert-Butyl Isocyanide, and Trimethylsilyl Azide: Diazo, Cyano, and Imido Complexes. / Herrmann, Wolfgang A.; Menj, Babilin; Herdtweck, Eberhardt.
In: Organometallics, Vol. 10, No. 7, 01.07.1991, p. 2134-2141.

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

TY - JOUR

T1 - Chemistry of Oxophilic Transition Metals. 4. Reactivity of the Organozirconium(III) Complex (μ-η5:η5-C10H8)[(μ-Cl)Zr(η5-C5H5)]2 with Diphenyldiazomethane, tert-Butyl Isocyanide, and Trimethylsilyl Azide

T2 - Diazo, Cyano, and Imido Complexes

AU - Herrmann, Wolfgang A.

AU - Menj, Babilin

AU - Herdtweck, Eberhardt

PY - 1991/7/1

Y1 - 1991/7/1

N2 - The fulvalene zirconium(III) complex (μ-η5:η5-C10H8)[(μ-Cl)Zr(η5-C5H5)]2 (1) reacts with stoichiometric amounts of diphenyldiazomethane, N2=C(C6H5)2, and with tert-butyl isocyanide, C≡NC(CH3)3, to give the 1:1 addition products [μ-η1:η2-N2(C6H5)2](μ-η5:η5-C10H8)[(η5-C5H5)ZrCl]2 (3) and [μ-η1:η2-CNC-(CH3)3](μ-η5:η5-C10H8)[(η5-C5H5)ZrCl]2 (4), respectively. On the other hand, the reaction of 1 with trimethylsilyl azide, (CH3)3SiN3, takes place under loss of molecular nitrogen, yielding a mixture of (μ-η5:η5-C10H8)[(η5-C5H5)ZrCl2]2 (5) and (μ-η5:η5-C10H8)(μ-NSUCH3)3Zr(η5-C5H5)]2 (6). The crystal and molecular structures of 3 and 4 have been determined by X-ray diffraction methods. 3 crystallizes in a triclinic unit cell of PI symmetry with a = 9.189 (1) Å, b = 10.808 (1) Å, c = 15.833 (1) Å, α = 104.93 (1)°, ß = 100.35 (1)°, γ = 97.82 (1)°, V = 1467 Å3, Z = 2, and dcalc = 1.598 g cm−3. 4 crystallizes in an orthorhombic crystal lattice of P212121 symmetry with a = 8.233 (1) Å, b = 16.891 (2) Å, c = 17.312 (2) Å, V = 2407 Å3, Z = 4, and dcalc = 1.641 g cm−3. Both structures can be regarded as a result of diphenyldiazomethane and tert-butyl isocyanide insertion into the Zr-Zr bond of 1 with concomitant splitting (opening) of the chloride bridges. The unsaturated organic molecule acts as a bridging ligand, coordinated in a (σ + π) fashion. Sodium amalgam reduction of 4 in the presence of C≡NC(CH3)3 unexpectedly yields the cyano complex (μ-η5:η5-C10H8)[(μ-η1:η2-CN)(η5-C5H5)]2 (8), whose structure has been inferred from IR and 1H and 13C NMR spectroscopic data.

AB - The fulvalene zirconium(III) complex (μ-η5:η5-C10H8)[(μ-Cl)Zr(η5-C5H5)]2 (1) reacts with stoichiometric amounts of diphenyldiazomethane, N2=C(C6H5)2, and with tert-butyl isocyanide, C≡NC(CH3)3, to give the 1:1 addition products [μ-η1:η2-N2(C6H5)2](μ-η5:η5-C10H8)[(η5-C5H5)ZrCl]2 (3) and [μ-η1:η2-CNC-(CH3)3](μ-η5:η5-C10H8)[(η5-C5H5)ZrCl]2 (4), respectively. On the other hand, the reaction of 1 with trimethylsilyl azide, (CH3)3SiN3, takes place under loss of molecular nitrogen, yielding a mixture of (μ-η5:η5-C10H8)[(η5-C5H5)ZrCl2]2 (5) and (μ-η5:η5-C10H8)(μ-NSUCH3)3Zr(η5-C5H5)]2 (6). The crystal and molecular structures of 3 and 4 have been determined by X-ray diffraction methods. 3 crystallizes in a triclinic unit cell of PI symmetry with a = 9.189 (1) Å, b = 10.808 (1) Å, c = 15.833 (1) Å, α = 104.93 (1)°, ß = 100.35 (1)°, γ = 97.82 (1)°, V = 1467 Å3, Z = 2, and dcalc = 1.598 g cm−3. 4 crystallizes in an orthorhombic crystal lattice of P212121 symmetry with a = 8.233 (1) Å, b = 16.891 (2) Å, c = 17.312 (2) Å, V = 2407 Å3, Z = 4, and dcalc = 1.641 g cm−3. Both structures can be regarded as a result of diphenyldiazomethane and tert-butyl isocyanide insertion into the Zr-Zr bond of 1 with concomitant splitting (opening) of the chloride bridges. The unsaturated organic molecule acts as a bridging ligand, coordinated in a (σ + π) fashion. Sodium amalgam reduction of 4 in the presence of C≡NC(CH3)3 unexpectedly yields the cyano complex (μ-η5:η5-C10H8)[(μ-η1:η2-CN)(η5-C5H5)]2 (8), whose structure has been inferred from IR and 1H and 13C NMR spectroscopic data.

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U2 - 10.1021/om00053a015

DO - 10.1021/om00053a015

M3 - Article

AN - SCOPUS:0001700442

SN - 0276-7333

VL - 10

SP - 2134

EP - 2141

JO - Organometallics

JF - Organometallics

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