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)

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).

[1]  J. Weidlein,et al.  Base‐freie Tris(trimethylsilyl)methyl‐Derivate des Lithiums, Aluminiums, Galliums und Indiums , 1997 .

[2]  W. Schwarz,et al.  1,2-bis(dimethylamino) ethan-komplexe von heteroleptischen alkylzink-verbindungen: Zusammenhang zwischen ZnN-abstand und RZnR′-bindungswinkel , 1996 .

[3]  C. Eaborn,et al.  Compounds of elements of Groups 11–13 containing (Me3Si)3C, (PhMe2Si)3C or related ligands , 1996 .

[4]  H. Vahrenkamp,et al.  Zinkkomplexe von Bis(imidazolylmethyl)sulfiden und ‐oxiden , 1994 .

[5]  W. Schwarz,et al.  Heteroleptische diorganylzink-verbindungen des typs (Me3Si)3CZnR , 1994 .

[6]  J. Weidlein,et al.  Die Röntgenstrukturanalyse der Pyrrolide (CH3)2Al - C4H3NCH3 und (CH3)2Ga - N(CCH3)4 / The X-Ray Structure Determination of the Pyrrolides (CH3)2Al - C4H3NCH3 and (CH3)2Ga - N(CCH3)4 , 1994 .

[7]  H. Hausen,et al.  [(CH3C)4N-(CH3)2Al · · · Cl · · · Al(CH3)2 -N(CCH3)4]Li - ein ungewo¨hnlicher sandwich-komplex des lithiums , 1994 .

[8]  A. Habtemariam,et al.  The preparation and crystal structures of the compounds (Ph2MeSi)3CMCl (M = Zn, Cd, or Hg) , 1993 .

[9]  A. Haaland,et al.  Dimethylmetallderivate substituierter Pyrrole (Metall = Al, Ga und In) / Dimethylmetal Derivatives of Substituted Pyrroles (Metal = Al, Ga, and In) , 1993 .

[10]  W. Herrmann,et al.  Kristall‐ und Molekülstruktur von Bis(pyridin)bis(trifluoromethyl)zink , 1993 .

[11]  A. Sebald,et al.  Mixed amide thiolate complexes of zinc with low coordination number at the metal atom , 1992 .

[12]  G. Henkel,et al.  2,2′,5,5′-Tetra-tert-butyl-1,1′-diazaplumbocene— a Stable Azacyclopentadienyl Compound of Lead†‡ , 1992 .

[13]  N. Kuhn,et al.  2,2′,5,5′‐Tetra‐tert‐butyl‐1,1′‐diazaplumbocen — eine stabile Azacyclopentadienyl‐Verbindung des Bleis , 1992 .

[14]  G. Rossetto,et al.  Diethylindium(III) derivatives: Synthesis and characterization of diethylindium(III) dialkylamides and diethylindium(III) pyrrolide. X-Ray crystal structures of diethylindium(III) pyrrolide and diethylindium(III) bromide , 1992 .

[15]  W. S. Rees,et al.  Synthesis and X-ray diffraction crystal structure of Zn{N[(C(CH3)3)(Si(CH3)3)]}2. The first solid-state characterization of a homoleptic zinc amide , 1992 .

[16]  M. Westerhausen,et al.  Trimethylsilyl-substituierte Derivate des Dimethylzinks — Synthese, spektroskopische Charakterisierung und Struktur , 1991 .

[17]  P. Power,et al.  Synthesis and characterization of the isoelectronic d10 species bis[bis(methyldiphenylsilyl)amido]cuprate(1-) and -zinc , 1991 .

[18]  G. Henkel,et al.  2,3,4,5‐Tetramethyl‐1‐sodiopyrrole: An Azacyclopentadienyl Ligand in a Novel Bridging Function , 1990 .

[19]  N. Kuhn,et al.  2,3,4,5‐Tetramethyl‐1‐natriopyrrol — ein Azacyclopentadienyl‐Ligand in neuartiger Brückenfunktion , 1990 .

[20]  E. Horn,et al.  Heterocyclen als Liganden, VI: Die verbrückende Koordination eines 1,1′-Diazaferrocens in einem zweikernigen Silberkomplex — eine ungewöhnliche Struktur , 1989 .

[21]  G. Koten,et al.  The unusual solid state structures of the pentasubstituted bis(cyclopentadienyl)zinc compounds bis(pentamethylcyclopentadienyl)zinc and bis(tetramethylphenylcyclopentadienyl)zinc , 1989 .

[22]  C. Janiak,et al.  Synthesis and crystal structure of pentabenzylcyclopentadienylindium(I) , 1989 .

[23]  O. T. Beachley,et al.  (Pentamethylcyclopentadienyl)indium(I) and -indium(III) compounds: syntheses, reactivities, and X-ray diffraction and electron diffraction studies of In(C5Me5) , 1989 .

[24]  B. V. Lokshin,et al.  Vibrational spectra and structure of indium and thallium monocyclopentadienyl complexes , 1988 .

[25]  P. V. R. Schleyer,et al.  Die Röntgenstruktur von N-Lithiocarbazol-Dimer: Experimentelle Bestätigung der theoretischen Analyse von Strukturen des N-Lithiopyrrol-Typs , 1987 .

[26]  A. Rheingold,et al.  Synthesis, structure, and reactions of a dimeric rhodium(I) complex with bridging σ- and π-bonded 2,5-dimethylpyrrolido ligands , 1987 .

[27]  R. Blom,et al.  The preparation of bis(pentamethylcyclopentadienyl) zinc and bis (trimethylsilylcyclopentadienyl) zinc, and their molecular structures determined by gas electron diffraction , 1986 .

[28]  A. Spek,et al.  The structure of dicyclopentadienylzinc , 1985 .

[29]  P. Budzelaar,et al.  A novel type of cyclopentadienyl bridge-structure of (.mu.-C5H5)[.mu.-N(SiMe3)2](ZnC5H5)2 , 1984 .

[30]  P. Power,et al.  Molecular structure of bis[bis(trimethylsilyl)amino]zinc as determined by gas electron diffraction , 1984 .

[31]  J. Boersma.  16 – Zinc and Cadmium , 1982 .

[32]  N. Retta,et al.  Di[tris(trimethysilyl)methyl]-zinc and -cadmium☆ , 1980 .

[33]  W. Herrmann,et al.  Chemie der Übergangsmetall‐Heterocyclen‐Komplexe, I. Über eine elektrophile Pyrrolyl‐Eliminierung aus Azacymantren , 1979 .

[34]  K. Wade,et al.  The Crystal and Molecular Structure of Cyclopentadienylzinc methyl, Zn(C5H5)Me , 1978 .

[35]  D. T. Cromer,et al.  X-ray scattering factors computed from numerical Hartree–Fock wave functions , 1968 .

[36]  William T. Simpson,et al.  Coherent X‐Ray Scattering for the Hydrogen Atom in the Hydrogen Molecule , 1965 .

[37]  R. King,et al.  Organometallic Chemistry of the Transition Metals. VIII. π-Cyclopentadienyl-π-pyrrolyliron and π-Cyclopentadienyl-π-indenyliron , 1964 .

[38]  R. F. Barrow,et al.  The heats of sublimation of inorganic substances. Part 6.—Some halides of gallium and indium , 1958 .