Molecular structure of bis[bis(trimethylsilyl)amino]zinc as determined by gas electron diffraction

Haaland, Arne; Hedberg, Kenneth; Power, Philip P.

doi:10.1021/ic00181a036

Cited by 62 publications

(29 citation statements)

References 2 publications

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“…[17] The pyrrolide substituent in 3 is planar and shows a different coor-(185 pm), in monomeric zinc bis(amides) [18] (characteristic value 182 pm), or even in bridging µ-bonded bis(trimethyldination behavior. Both the zinc atoms coordinate at the same side of the ligand, but one zinc atom bonds via a silyl)amide substituents, where ZnϪN distances of approximately 200 pm are found.…”

Section: The Pyrrolide Substituent [Nc 4 H 4 ]mentioning

confidence: 99%

Coordination Modes of 2,5-Di(tert-butyl)pyrrolide – Crystal Structures of HPyr, PyrH·thf, (thf)2LiPyr, and [(Me3Si)3C-Zn]2(μ-Cl)(μ-Pyr) (Pyr* = 2,5-tBu2NC4H2)

Westerhausen¹,

Wieneke²,

Nöth³

et al. 1998

Eur. J. Inorg. Chem.

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The lithiation of 2,5‐di(tert‐butyl)pyrrole (1) yields bis(tetrahydrofuran)lithium 2,5‐di(tert‐butyl)pyrrolide (2), which is monomeric in solution as well as in the solid state. Due to the coordination number of three for the lithium atom, short Li–O and Li–N bond lengths of 193 pm are observed. The metathesis reaction of 2 with tris(trimethylsilyl)‐methylzinc chloride (3) gives colorless bis[tris(trimethyl‐silyl)methylzinc] chloride 2,5‐di(tert‐butyl)pyrrolide (4). The pyrrolide ligand and the chlorine atom bridge the zinc atoms. One of the zinc atoms is bonded to the nitrogen atom of the pyrrolide substituent, while the other bonds to the opposite C–C bond. At 215 pm, the Zn–N bond is very long compared to those in alkylzinc amides, whereas the Zn–C distances lie in the range of Zn–C bond lengths found between zinc and η5‐bonded cyclopentadienide ligands. The molecular structures of 1 and of the low‐melting THF adduct 1·thf show a similar 2,5‐di(tert‐butyl)pyrrole molecule, but in the latter case a weak N–H···O bond is observed (N–H 97 pm, O···H 199 pm).

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Section: The Pyrrolide Substituent [Nc 4 H 4 ]mentioning

confidence: 99%

Coordination Modes of 2,5-Di(tert-butyl)pyrrolide – Crystal Structures of HPyr, PyrH·thf, (thf)2LiPyr, and [(Me3Si)3C-Zn]2(μ-Cl)(μ-Pyr) (Pyr* = 2,5-tBu2NC4H2)

Westerhausen¹,

Wieneke²,

Nöth³

et al. 1998

Eur. J. Inorg. Chem.

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“…Sowohl dieser Befund als auch die im ^Sif'HJ-NM R-Spektrum beobachtete Hochfeldverschiebung deutet auf eine partielle Übertragung der Ladung auf die benach barten Siliciumatome hin. [20], Elektronenbeugung an der Gasphase), Bis(terr-butyl-trimethylsilylamino)zink (182 pm [21], Festkörper) und Bis[bis(methyl-diphenylsilyl)amino]zink (185 pm [22], Festkörper) und andererseits große L i-N -A bstände, verglichen mit trim erem (200 pm [23], Festkörper) oder dimerem Lithium-bis(trimethylsilyl)amid (199 pm [24], Elektronenbeugung an der Gasphase). Selbst in Komplexen des Typs XZn[//-N(SiMe3)2](w-X)ZnX mit dem Rest X als C5H 5 [25] Li-N -B indung hingegen läßt sich auf die höhere Koordinationszahl des Lithiumatoms zurück führen; bei zweifacher Koordination beobachtet man L i-N -A bstände von 200 pm [23,24], bei drei facher von 203 bis 206 pm [27,28] und bei der hier beschriebenen vierfachen von sogar 208 pm.…”

Section: Olekülstruktur Von 3 Aunclassified

Lithium-zinkate mit heteroleptischem Triorganylzinkat-Anion / Lithium Zincates with Heteroleptic Triorganylzincate Anion

Westerhausen

Rademacher

Schwarz

et al. 1994

Zeitschrift Für Naturforschung B

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Lithium Zincate, Heteroleptic Triorganylzincate, Zincate, X-Ray, NMR Spectra Bis(trimethylsilylmethyl)-, bis[bis(trimethylsilyl)methyl]-as well as bis (2,2,4,4,6,6-hexamethyl-2,4,6-trisila-cyc/o-hexyl)zinc react with methyl lithium or phenyl lithium in the pres ence of the tridentate l,3,5-trimethyl-l,3,5-triazinane (TMTA) to yield zincates of the type LiZnR2R'-2TMTA. The compounds are colorless and insoluble in aliphatic or aromatic hydrocarbons. These zincates exist in solution as well as in the crystalline state as separated ions, as confirmed for lithium-methyl-bis(2,2,4,4,6,6-hexamethyl-2,4,6-trisila-cyc/o-hexyl)-zincate• 2TMTA by X-ray diffraction (PI; a -1139,5(3); b = 1482,4(4); c = 1528,6(5) pm; a = 95,33(2); ß = 100,13(2); y = 106,91(2)°; Z = 2). The lithium cation is six-coordinated by two TMTA ligands in a distorted anti-prismatic complex. The zinc atom displays a trigonal planar coordination with Z n -C bond lengths of 207 pm to the 2,2,4,4,6,6-hexamethyl-2,4,6-trisila-cyc/o-hexyl ligands and of 202 pm to the methyl group. One trisila-cyc/o-hexyl substi tuent exists in the chair, the other one in the twist conformation. The reaction of lithium bis(trimethylsilyl)amide with bis(trimethylsilylmethyl)zinc yields the benzene soluble lithium-bis(trimethylsilyl)amino-bis(trimethylsilylmethyl)zincate TMTA. The molecular structure was confirmed by X-ray diffraction a -1024,8(3); b = 1775,4(7), c = 1918,2(8) pm; Z = 4). The bridging bis(trimethylsilyl)amino ligand displays long Z n -N and L i-N distances of 213 and 208 pm, respectively, due to the steric inter-ligand repulsion. During the reaction of lithium bis(trimethylsilyl)amide with bis[bis(trimethylsilyl)methyl]-zinc no zincate formations observed. The decomposition products lithium bis(trimethylsilyl)-methanide and the heteroleptic bis(trimethylsilyl)amino-bis(trimethylsilyl)methylzinc were detected.Einleitung

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“…The Zn-N3 bond length to the bis(trimethylsilyl)amido group shows a value of 189.3(2) pm which is larger than observed for homoleptic Zn[N(SiMe 3 ) 2 ] 2 with a two-coordinate zinc atom [X-ray diffraction, solid state: 183(1) pm; electron diffraction, gas phase: 182(1) pm [34] ]. Enhancement of the coordination number to three in [(Me 3 Si) 2 N-Zn(µ-OCEt 3 )] 2 gives Zn-N bonds lengths of 186.8(3) pm.…”

Section: Molecular Structuresmentioning

confidence: 87%

Lithium and Zinc Complexes of C‐ and N‐Functionalized (2‐Pyridylmethyl)amines

et al. 2008

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The addition reaction of benzophenone with lithium (2‐pyridylmethyl)(tert‐butyldimethylsilyl)amide yields dimeric1‐lithoxy‐1,1‐diphenyl‐2‐(2‐pyridyl)‐2‐(trialkylsilylamino)ethane (1) with formation of a C–C bond. C‐Functionalized 2‐(pyridylmethyl)amines are accessible via the reaction of N‐(2‐pyridylmethylidene)phenylamine with diethylmalonate giving 2,2‐bis(ethoxycarbonyl)‐1‐(phenylamino)‐1‐(2‐pyridyl)ethane (2) which eliminates aniline upon heating yielding diethyl 2‐(2‐pyridylmethylidene)malonate (3). The addition of piperidine leads to the formation of the Michael type adduct 2,2‐bis(ethoxycarbonyl)‐1‐piperidyl‐1‐(2‐pyridyl)ethane (4) which can be deprotonated with metal‐organic reagents such as Zn[N(SiMe3)2]2, Zn[CH(SiMe3)2]2, LiN(SiMe3)2, and NaN(SiMe3)2 leading to 2,2‐bis(ethoxycarbonyl)‐1‐piperidyl‐1‐(2‐pyridyl)ethane‐2‐yl complexes of zinc (5 and 6), lithium (7), and sodium (8). N‐Functionalization can be achieved via the reaction of (2‐pyridylmethyl)(trialkylsilyl)amine with benzoyl chloride giving N‐(2‐pyridylmethyl)benzoylamine (9). Lithiation and subsequent salt metathesis reaction with another equivalent of benzoyl chloride yields N‐(2‐pyridylmethyl)dibenzoylamine (10). The addition reaction of ZnCl2 with N‐(2‐pyridylmethyl)(diphenylmethylidene)amine (11) forms colorless crystalline [(Py–CH2N=CPh2)ZnCl2] (12). The addition of benzoyl chloride leads to N‐(diphenylchloromethyl)‐N‐(2‐pyridylmethyl)benzoylamine (13). Addition of ZnCl2 leads to the formation of solvent‐separated [(2‐pyridylmethyl)(benzoylamino)diphenylcarbonium] [(tetrahydrofuran)trichlorozincate] (14). The X‐ray crystal structures of 1, 4 to 7, 9, 12, and 14 are discussed.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Molecular structure of bis[bis(trimethylsilyl)amino]zinc as determined by gas electron diffraction

Cited by 62 publications

References 2 publications

Coordination Modes of 2,5-Di(tert-butyl)pyrrolide – Crystal Structures of HPyr, PyrH·thf, (thf)2LiPyr, and [(Me3Si)3C-Zn]2(μ-Cl)(μ-Pyr) (Pyr* = 2,5-tBu2NC4H2)

Coordination Modes of 2,5-Di(tert-butyl)pyrrolide – Crystal Structures of HPyr, PyrH·thf, (thf)2LiPyr, and [(Me3Si)3C-Zn]2(μ-Cl)(μ-Pyr) (Pyr* = 2,5-tBu2NC4H2)

Lithium-zinkate mit heteroleptischem Triorganylzinkat-Anion / Lithium Zincates with Heteroleptic Triorganylzincate Anion

Lithium and Zinc Complexes of C‐ and N‐Functionalized (2‐Pyridylmethyl)amines

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Molecular structure of bis[bis(trimethylsilyl)amino]zinc as determined by gas electron diffraction

Cited by 62 publications

References 2 publications

Coordination Modes of 2,5-Di(tert-butyl)pyrrolide – Crystal Structures of HPyr*, Pyr*H·thf, (thf)2LiPyr*, and [(Me3Si)3C-Zn]2(μ-Cl)(μ-Pyr*) (Pyr* = 2,5-tBu2NC4H2)

Coordination Modes of 2,5-Di(tert-butyl)pyrrolide – Crystal Structures of HPyr*, Pyr*H·thf, (thf)2LiPyr*, and [(Me3Si)3C-Zn]2(μ-Cl)(μ-Pyr*) (Pyr* = 2,5-tBu2NC4H2)

Lithium-zinkate mit heteroleptischem Triorganylzinkat-Anion / Lithium Zincates with Heteroleptic Triorganylzincate Anion

Lithium and Zinc Complexes of C‐ and N‐Functionalized (2‐Pyridylmethyl)amines

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Coordination Modes of 2,5-Di(tert-butyl)pyrrolide – Crystal Structures of HPyr, PyrH·thf, (thf)2LiPyr, and [(Me3Si)3C-Zn]2(μ-Cl)(μ-Pyr) (Pyr* = 2,5-tBu2NC4H2)

Coordination Modes of 2,5-Di(tert-butyl)pyrrolide – Crystal Structures of HPyr, PyrH·thf, (thf)2LiPyr, and [(Me3Si)3C-Zn]2(μ-Cl)(μ-Pyr) (Pyr* = 2,5-tBu2NC4H2)