Synthesis and molecular structure of (.eta.5-C5Me5)2Hf(H)(NHMe). Structural evidence for nitrogen-to-hafnium .pi.-donation

Hillhouse, Gregory L.; Bulls, A. Ray; Santarsiero, Bernard D.; Bercaw, John E.

doi:10.1021/om00096a012

Cited by 52 publications

(34 citation statements)

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“…The aromatic proton of the thiolate group appears at 5.49 ppm and the hydride signal at 5.95 ppm which agrees well with the shift expected according to that found in other hydridezirconocene complexes, like Cp* 2 ZrH(NH 2 ) 19 (4.83 ppm) or (Cp* 2 ZrH) 2 O 20 (5.50 ppm). It has been characterized by elemental analysis, 1 H and 13 C NMR, and IR spectroscopy.…”

Section: Table 1 Selected Bond Distances (å) and Angles (Deg) With Esupporting

confidence: 89%

Zirconium Alkyl Thiolate Complexes: Synthesis and Reactivity. Molecular Structures of [Zr(η⁵-C₅H₅)₂(η²-C₆H₇N₂S)(Me)] and [Zr(η⁵-C₅H₅)₂(η¹-C₆H₇N₂S)(η²-CH₃CNXylyl)] (Xylyl = 2,6-Dimethylphenyl)

et al. 1996

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The thiolate−alkylzirconocene complex Cp2ZrMe(SR) (2) (Cp = η5-C5H5; SR = 4,6-dimethylpyrimidine-2-thiolate) can be prepared by reacting the corresponding dialkylmetallocene complex Cp2ZrMe2 (1) with 1 equiv of 4,6-dimethyl-2-mercaptopyrimidine. X-ray structure analysis of complex 2 revealed that the thiolate group is bonded in an η2 fashion through the sulfur and one of the nitrogen atoms. Complex 2 reacts with 2,6-dimethylphenyl isocyanide (CNXylyl) to yield the corresponding iminoacyl derivative, Cp2Zr(η2-MeCNXylyl)(SR) (4). The molecular structure of 4 shows that the thiolate group is η1-bonded while the iminoacyl group behaves as a bidentate ligand. Reaction of compound 2 with different acidic reagents gives formation of methane and different zirconium complexes. Reaction with HSR renders Cp2Zr(SR)2 (3) and with (NHEt3)(BPh4) the cationic complex [Cp2Zr(SR)][BPh4] (5). An hydride thiolate complex, Cp*2ZrH(SR) (Cp* = η5-C5Me5) (6) can also be prepared by reaction of “Cp*2Zr” with HSR by an oxidative addition reaction.

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Section: Table 1 Selected Bond Distances (å) and Angles (Deg) With Esupporting

confidence: 89%

Zirconium Alkyl Thiolate Complexes: Synthesis and Reactivity. Molecular Structures of [Zr(η⁵-C₅H₅)₂(η²-C₆H₇N₂S)(Me)] and [Zr(η⁵-C₅H₅)₂(η¹-C₆H₇N₂S)(η²-CH₃CNXylyl)] (Xylyl = 2,6-Dimethylphenyl)

et al. 1996

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“…11 kcal/mol) 31 and Cp* 2 Hf(H)(NHMe) (Δ G ⧧ = ca. 10 kcal/mol) have been attributed to steric factors. On the other hand, electronic π-interactions may also be contributing to the observed hindered rotation.…”

Section: Resultsmentioning

confidence: 99%

Indenylnickel Imidato Complexes: Synthesis, Characterization, and Reactivities

et al. 1998

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The complex (1-Me-indenyl)Ni(PPh3)(phthalimidate) has been prepared and fully characterized by IR and 1H, 13C{1H}, and 31P{1H} NMR spectroscopy and single-crystal X-ray diffraction. The analogous 4,5-dichlorophthalimidato, maleimidato, and succinimidato complexes have also been prepared and characterized spectroscopically. These complexes are thermally stable, in contrast to the analogous Ni−amido species, which could not be prepared. Reactivity studies have shown that the Ni−imidato bond is fairly unreactive in insertion and nucleophilic reactions, and VT 1H NMR studies suggest that the rotation around the Ni−N bond in the maleimidato complex is hindered by ca. 11 kcal/mol. The solid-state structure of the phthalimidato derivative showed that the P, N, C1, and C3 atoms are arranged around the Ni atom in a distorted-square-planar coordination environment, while the C2 atom is within bonding distance above the main square plane. The phthalimidato ligand is η1(N)-coordinated to Ni; the Ni−N bond is relatively short (1.895(4) Å), and the orientation of the imidato ligand is such that the planes bearing the atoms P, Ni, N and C9, N, C16 are rotated by ca. 76° with respect to each other. The hapticity of the indenyl ligand is characterized by an allyl-ene distortion (η5↔η3) and a partial localization of bonding inside the indenyl ring (η3↔η1,η2). 1H and 13C{1H} NMR spectra indicate that the nonsymmetrical coordination of the indenyl ligand, which can be attributed to the different trans influences of the phthalimidato and PPh3 ligands, is maintained in the solution. The character of the Ni−imidato bond has been discussed in terms of electrostatic-covalent and π-bonding interactions.

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“…[15] Even though Cp 2 MϪN π-interactions are not maximized in group-4 amido [13] and ketimide [14] metallocene complexes, π-overlap between the LUMO of the metal fragment and the nitrogen lone pair has been commonly observed. Erker and co-workers have reported that aldimido [RCHϭ NϪZrCp 2 Cl] complexes have a substantial ZrϪN π-character.…”

Section: Discussionmentioning

confidence: 99%

Dynamic Behavior of an N‐Metalated β‐Enaminoimine Complex − Preparation of N‐Phosphanylenamine and β‐Enaminoimine Derivatives

et al. 2003

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Variable-temperature NMR spectroscopy of the β-enaminoimine complex 2 showed a dynamic process which was attributed to an internal fluxional aldimido N-zirconated π-linear/σ-bent structure. Such an internal rearrangement has been previously proposed to occur in these systems but never observed. We have prepared a variety of (N-phosphanyl-β-enamino)imine ligands using the hydrozirconation/transmetalation reaction of malonodinitrile compounds RCH(CN) 2

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Synthesis and molecular structure of (.eta.5-C5Me5)2Hf(H)(NHMe). Structural evidence for nitrogen-to-hafnium .pi.-donation

Cited by 52 publications

References 0 publications

Zirconium Alkyl Thiolate Complexes: Synthesis and Reactivity. Molecular Structures of [Zr(η⁵-C₅H₅)₂(η²-C₆H₇N₂S)(Me)] and [Zr(η⁵-C₅H₅)₂(η¹-C₆H₇N₂S)(η²-CH₃CNXylyl)] (Xylyl = 2,6-Dimethylphenyl)

Zirconium Alkyl Thiolate Complexes: Synthesis and Reactivity. Molecular Structures of [Zr(η⁵-C₅H₅)₂(η²-C₆H₇N₂S)(Me)] and [Zr(η⁵-C₅H₅)₂(η¹-C₆H₇N₂S)(η²-CH₃CNXylyl)] (Xylyl = 2,6-Dimethylphenyl)

Indenylnickel Imidato Complexes: Synthesis, Characterization, and Reactivities

Dynamic Behavior of an N‐Metalated β‐Enaminoimine Complex − Preparation of N‐Phosphanylenamine and β‐Enaminoimine Derivatives

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Synthesis and molecular structure of (.eta.5-C5Me5)2Hf(H)(NHMe). Structural evidence for nitrogen-to-hafnium .pi.-donation

Cited by 52 publications

References 0 publications

Zirconium Alkyl Thiolate Complexes: Synthesis and Reactivity. Molecular Structures of [Zr(η5-C5H5)2(η2-C6H7N2S)(Me)] and [Zr(η5-C5H5)2(η1-C6H7N2S)(η2-CH3CNXylyl)] (Xylyl = 2,6-Dimethylphenyl)

Zirconium Alkyl Thiolate Complexes: Synthesis and Reactivity. Molecular Structures of [Zr(η5-C5H5)2(η2-C6H7N2S)(Me)] and [Zr(η5-C5H5)2(η1-C6H7N2S)(η2-CH3CNXylyl)] (Xylyl = 2,6-Dimethylphenyl)

Indenylnickel Imidato Complexes: Synthesis, Characterization, and Reactivities

Dynamic Behavior of an N‐Metalated β‐Enaminoimine Complex − Preparation of N‐Phosphanylenamine and β‐Enaminoimine Derivatives

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Zirconium Alkyl Thiolate Complexes: Synthesis and Reactivity. Molecular Structures of [Zr(η⁵-C₅H₅)₂(η²-C₆H₇N₂S)(Me)] and [Zr(η⁵-C₅H₅)₂(η¹-C₆H₇N₂S)(η²-CH₃CNXylyl)] (Xylyl = 2,6-Dimethylphenyl)

Zirconium Alkyl Thiolate Complexes: Synthesis and Reactivity. Molecular Structures of [Zr(η⁵-C₅H₅)₂(η²-C₆H₇N₂S)(Me)] and [Zr(η⁵-C₅H₅)₂(η¹-C₆H₇N₂S)(η²-CH₃CNXylyl)] (Xylyl = 2,6-Dimethylphenyl)