Synthesis and crystal structures of dinuclear zinc complexes with the 1,3-bis(2-pyridylmethyl)acetamidinato ligand

Kahnes, Marcel; Görls, Helmar; Westerhausen, Matthias

doi:10.1016/j.jorganchem.2011.01.033

Cited by 13 publications

(12 citation statements)

References 51 publications

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“…Only a few crystal structures of similar monozinc hydride complexes have previously been reported. The Zn−H distances are as follows: (tris(2-pyridylthio)methane)zinc hydride, 1.51(3) Å; 17 (tris(4,4-dimethyl-2oxazolinyl)phenylborate)zinc hydride, 15 1.525 (16) 21 , 1.49(2) Å. The distance of 1.75(3) Å seen in 10 is significantly longer than all of these.…”

Section: ■ Results and Discussionmentioning

confidence: 96%

“…1a,18 These complexes exhibit a range of structures, including clusters, 15 cubanes, 6,11,13 dimers, 1c,12a,14,17,19 and mononuclear structures. 2b,9b,12d,16,18 The carbon dioxide insertion chemistry of only a few of these hydride complexes has been studied.…”

Section: Introductionmentioning

confidence: 99%

“…Various zinc hydride complexes, of the formulation LZnH, have been reported where L, a monoanionic ancillary ligand, is selected from amino/pyridyl amides, , tris(pyrazoyl)hydroborates, , 3,5-disubstituted pyrazoles, phosphorane iminates, β-diketiminates, alkoxides, , 2,6-dialkylphenyls, pyridyl-substituted tris(trimethylsilyl)methanides, tris(4,4-dimethyl-2-oxazolinyl)phenylborate, , acetimidinato, and tris(2-pyridylthio)methyl. , These complexes exhibit a range of structures, including clusters, cubanes, ,, dimers, ,,,, and mononuclear structures. ,,,, The carbon dioxide insertion chemistry of only a few of these hydride complexes has been studied. The tetranuclear cubane hydrido zinc alkoxide complexes insert carbon dioxide slowly, but the reaction is accelerated by substituting one zinc vertex of the cube with a lithium ion .…”

Section: Introductionmentioning

confidence: 99%

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Mononuclear Phenolate Diamine Zinc Hydride Complexes and Their Reactions With CO₂

et al. 2014

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The synthesis, characterization, and zinc coordination chemistry of the three proligands 2-tert-butyl-4-[tert-butyl (1)/methoxy (2)/nitro (3)]-6-{[(2′-dimethylaminoethyl)methylamino]methyl}phenol are described. Each of the ligands was reacted with diethylzinc to yield zinc ethyl complexes 4–6; these complexes were subsequently reacted with phenylsilanol to yield zinc siloxide complexes 7–9. Finally, the zinc siloxide complexes were reacted with phenylsilane to produce the three new zinc hydride complexes 10–12. The new complexes 4–12 have been fully characterized by NMR spectroscopy, mass spectrometry, and elemental analyses. The structures of the zinc hydride complexes have been probed using VT-NMR spectroscopy and X-ray diffraction experiments. These data indicate that the complexes exhibit mononuclear structures at 298 K, both in the solid state and in solution (d8-toluene). At 203 K, the NMR signals broaden, consistent with an equilibrium between the mononuclear and dinuclear bis(μ-hydrido) complexes. All three zinc hydride complexes react rapidly and quantitatively with carbon dioxide, at 298 K and 1 bar of pressure over 20 min, to form the new zinc formate complexes 13–15. The zinc formate complexes have been analyzed by NMR spectroscopy and VT-NMR studies, which reveal a temperature-dependent monomer–dimer equilibrium that is dominated by the mononuclear species at 298 K.

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Section: ■ Results and Discussionmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Mononuclear Phenolate Diamine Zinc Hydride Complexes and Their Reactions With CO₂

et al. 2014

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“… Westerhausen and coworkers prepared the amido-pyridine zinc(II) hydride adducts [{RZn} 2 {μ-N(CH 2 Py) 2 }(μ-H)] (R = Me, CH 2 SiMe 3 , CH(SiMe 3 ) 2 ; Py = 2-pyridyl, 386 – 388 ) with the trimethylsilylmethyl derivative ( 387 ) undergoing a subsequent partial dismutation reaction to afford the pentanuclear Zn complex [{Me 3 SiCH 2 Zn} 2 {μ-N(CH 2 Py) 2 }] 2 {Zn(μ-H) 2 } ( 389 ) (Scheme ). Structural variants of 386 – 388 were later prepared, supported by the monoanionic tetradentate pyridyl-formamidinate ligand [PyCH 2 NC(Me)NCH 2 Py] − . A standout in amidozinc hydride chemistry is Jones’ two-coordinate zinc complex [{Ar* iPr (Me 3 Si)N}ZnH] ( 390 ) [Ar* iPr = 2,6,4-(Ph 2 CH) 2 i PrC 6 H 2 ], which was prepared by the addition of excess NaH to the zinc(II) bromide precursors [{Ar* iPr (Me 3 Si)N}ZnBr(THF) 0 or 1 ] ( 391 ) (eq 52 ).…”

Section: Molecular Hydrides Of Group 12 Metals (Zinc Cadmium and Merc...mentioning

confidence: 99%

Molecular Main Group Metal Hydrides

et al. 2021

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This review serves to document advances in the synthesis, versatile bonding, and reactivity of molecular main group metal hydrides within Groups 1, 2, and 12−16. Particular attention will be given to the emerging use of said hydrides in the rapidly expanding field of Main Group element-mediated catalysis. While this review is comprehensive in nature, focus will be given to research appearing in the open literature since 2001.

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“…The most significant reactivity of [κ 3 -Tism Pr i Benz ]CdN(SiMe 3 ) 2 , however, is that with PhSiH 3 to afford the cadmium hydride complex, [κ 3 -Tism Pr i Benz ]CdH (Scheme ). In addition, [κ 3 -Tism Pr i Benz ]CdH can also be obtained by reaction of [Tism Pr i Benz ]CdOSiPh 3 with PhSiH 3 (Scheme ). The use of a hydrosilane to afford a cadmium hydride complex is quite distinct from those approaches that involve metathesis of a cadmium halide complex with alkali metal hydride or borohydride derivatives. ,, …”

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confidence: 99%

Synthesis, Structure, and Reactivity of a Terminal Cadmium Hydride Compound, [κ³-Tism^PrⁱBenz]CdH

2021

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The terminal cadmium hydride compound, [κ3-TismPriBenz]CdH, which features the tris[(1-isopropylbenzimidazol-2-yl)dimethylsilyl]methyl ligand, may be obtained via the reactions of either [κ3-TismPriBenz]CdN(SiMe3)2 or [TismPriBenz]CdOSiPh3 with PhSiH3. The Cd–H bond of [κ3-TismPriBenz]CdH undergoes (a) metathesis reactions with MeI, Me3SiX (X = Cl, Br, I, NCO), and Me3SnX (X = Cl, Br, I) to afford the corresponding [TismPriBenz]CdX derivative, (b) insertion with CO2 and CS2 to afford respectively [TismPriBenz]Cd(κ1-O2CH) and [TismPriBenz]Cd(κ1-S2CH), and (c) hydride abstraction with B(C6F5)3 to afford {[TismPriBenz]Cd}[HB(C6F5)3] that possesses a rare trigonal monopyramidal geometry for cadmium.

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Synthesis and crystal structures of dinuclear zinc complexes with the 1,3-bis(2-pyridylmethyl)acetamidinato ligand

Cited by 13 publications

References 51 publications

Mononuclear Phenolate Diamine Zinc Hydride Complexes and Their Reactions With CO₂

Mononuclear Phenolate Diamine Zinc Hydride Complexes and Their Reactions With CO₂

Molecular Main Group Metal Hydrides

Synthesis, Structure, and Reactivity of a Terminal Cadmium Hydride Compound, [κ³-Tism^PrⁱBenz]CdH

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Synthesis and crystal structures of dinuclear zinc complexes with the 1,3-bis(2-pyridylmethyl)acetamidinato ligand

Cited by 13 publications

References 51 publications

Mononuclear Phenolate Diamine Zinc Hydride Complexes and Their Reactions With CO2

Mononuclear Phenolate Diamine Zinc Hydride Complexes and Their Reactions With CO2

Molecular Main Group Metal Hydrides

Synthesis, Structure, and Reactivity of a Terminal Cadmium Hydride Compound, [κ3-TismPriBenz]CdH

Contact Info

Product

Resources

About

Mononuclear Phenolate Diamine Zinc Hydride Complexes and Their Reactions With CO₂

Mononuclear Phenolate Diamine Zinc Hydride Complexes and Their Reactions With CO₂

Synthesis, Structure, and Reactivity of a Terminal Cadmium Hydride Compound, [κ³-Tism^PrⁱBenz]CdH