π-Bonding to tetravalent main-group IV elements; an experimental effort

doi:10.1016/0022-328X(89)87164-5

Journal of Organometallic Chemistry

Volume 365, Issues 1–2, 11 April 1989, Pages 37-46

In memoriam Professor Dr. Jerold J. Zuckerman.

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Abstract

Ph₅C₅GeCl₃ (1) and Ph₅C₅SnCl₃ (2) have been synthesized by oxidative addition of Ph₅C₅Cl to GeCl₂ or SnCl₂, respectively, and were characterized by ¹³C NMR and mass spectroscopy. Both compounds are fluxional in solution. The crystal structure 1 · 0.5Et₂O has been determined. 1 · 0.5Et₂O crystallizes in the space group C2/c with a 21.988(4), b 15.484(4), c 19.913(3) Å, β 111.411(14)°, V 6312(4) Å³, and Z=8. Solution of the structure led to final values of R=0.0303 (R_w = 0.0395) for 4989 observed reflections with F_o² ⩾ 3σ(F_o²). The germanium is σ-bonded to the pentaphenylcyclopentadienyl ligand.

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Penta-arylcyclopentadienyl complexes
2011, Coordination Chemistry Reviews
Citation Excerpt :
The structure of the ligand precursor, [C5(p-tol)5Br] (8, Fig. 10), is similar to that of the analogous C5Ph5Br (3) [32]. More recent chemistry that substitutes the cyclopentadienyl ring with alkyl-substituted aryl groups that increase solubility (i.e. C5Ar5H, Ar = 3,5-Bu2tC6H3 (9) [39], 3,5-Me2C6H3 (10) [40], 4-BunC6H4 (11)) [41] allows for insight into solution structures and solution dynamics, especially those pertaining to the alkali metal salts of penta-arylcyclopentadiene [39,42]. C5Ar5H (Ar = 3,5-Bu2tC6H3 (9), 3,5-Me2C6H3 (10)) may be easily deprotonated by BunLi in Et2O or THF, and multinuclear NMR spectroscopy performed upon the resultant [LiC5Ar5] species (Ar = 3,5-Bu2tC6H3 (12), 3,5-Me2C6H3 (13)) salts suggested free rotation of the aryl groups in solution.
This review covers the coordination and general chemistry of the 1,2,3,4,5-penta-arylcyclopentadiene system, as anion, C₅Ar₅⁻, radical, C₅Ar₅, and cation, C₅Ar₅⁺, as well as the neutral diene, C₅Ar₅H, and its derivatives. The structural rigidity and steric saturation offered by the penta-arylcyclopentadienyl ligand give rise to definite structural and geometric properties in its complexes that distinguish its chemistry from that of the parent cyclopentadiene.
The preparation, crystal structure and some reaction chemistry of Bromo (η5-penta- phenylcyclopentadienyl) dicarbonylosmium (II) , [Os (η5-C5Ph5) (CO) 2Br]
1998, Polyhedron
The preparation and characterisation of [Os (η⁵-C₅Ph₅) (CO) ₂Br] (1) are described ; this complex is the first reported C₅Ph⁻₅ derivative of osmium. A single crystal X-ray diffraction study of (1) (refined to R = 0.040, R_w = 0.043) is also reported. The related complexes, [Os {η⁵-C₅Ph₄ ( p-^tBuC₆H₄) } (CO) ₂Br] (2) and [Os {η⁵-C₅ ( p-MeC₆H₄) ₅} (CO) ₂Br] (3) , have also been prepared. Carbonyl substitution of (1) in tetrahydrofuran following treatment with Me₃NO afforded [Os (η⁵-C₅Ph₅) (CO) (L) Br] (L = PMe₂Ph (4) , P (OEt) ₃ (5) , P (OCH₂) ₃CCH₃ (6) and ^tBuNC (7) ) . A single crystal X-ray diffraction study of (6) (refined to R = 0.066, R_w = 0.073) is described.
The molecular structure of organogermanium compounds
1995, Coordination Chemistry Reviews
The crystal and molecular structure of (η5-pentaphenylcyclopentadienyl) (η5-cyclopentadienyl)iron(II), 1,2,3,4,5-pentaphenylferrocene, [Fe(C<inf>5</inf>Ph<inf>5</inf>)(C<inf>5</inf>H<inf>5</inf>)]
1993, Polyhedron
The preparation and characterization of [Fe(C₅Ph₅)(C₅H₅)] by single-crystal X-ray diffraction are reported. The compound crystallizes from chlorobenzene as a chlorobenzene solvate. The (C₅H₅) ring is planar to within 0.002 Å, whilst the C₅ ring of the (C₅Ph₅) ligand is planar to within 0.004 Å. The Fe—(ring centroid)_distances are both 1.652 Å. The phenyl substituents of the (C₅Ph₅) ring are canted relative to the cyclopentadienyl frame at angles between 44.3° and 61.8°. The structure of [Fe(C₅Ph₅)(C₅H₅)] is compared with the structures of ferrocene, 1,2,3,4,5-pentamethylferrocene and 1,2,3,4,5-penta(p-tolyl) ferrocene. The synthesis and characterization of [Fe(C₅Ph₅)(CO)₂]₂ is also reported. [Fe(C₅Ph₅)(CO)₂]₂ is assigned a trans configuration on the basis of its IR spectrum.
Bulky or Supracyclopentadienyl Derivatives in Organometallic Chemistry
1991, Advances in Organometallic Chemistry
This chapter focuses on supracyclopentadienyl derivatives in organometallic chemistry. Within organometallic chemistry—synthetic, analytical, physical, applied, and theoretical chemists are involved in research projects, dealing with highly substituted cyclopentadienylide (Cp)-metal complexes. Supra-Cp's are a major focus of this chapter, whereas for many others they are just a sideline where the bulkiness is a minor feature in the comparative study of certain phenomena. This chapter reveals unifying interest, sometimes with no cross-referencing to similar bulky Cp systems or even different metals carrying the same supra-Cp. The basic bulky Cp systems that are common in organometallic chemistry are discussed in the chapter, in their anionic form as ball-and-stick models with the hydrogens included. Other basic bulky Cp's described in the chapter are di(isobutyl)(tert-buty1)-Cp, penta(isopenty1)- Cp [isopentyl=( H,C2)2CH-], and tris(methoxycarbony1)-Cp. This chapter presents highly substituted Cp's, supracyclopentadienes that so far have escaped attention as ligands in organometallic complexes: tetra(terfbuty1)- Cp, 3,Mimethyl- and 3,5di-n-propyl- 1,2,4-triphenyl-Cp, and 1,2,3,5-tetraphenyl-4-p(7-cycloheptatrienyl)phenyl-Cp. Most of the bulky ring substituents are simple hydrocarbon moities, either alkyl or aryl groups, and consequently the supra-Cp's can be divided into two classes: peralkyl and peraryl systems. The use of bulky cyclopentadienes with functional group substituents causes problems in organometallic synthesis. Although there is a sizable number of Cp- metal complexes with only one functional group on the Carbon, ring examples for persubstituted systems are limited. This chapter also covers tetrasubstituted fulvalenes ethylene-bridged bis(tetrahydroindeny1) complexes and a dibornacyclopentadienyl ligand.
Circumambulatory rearrangements of cyclopolyenes containing element-centred migrants
2003, Russian Chemical Reviews

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Journal of Organometallic Chemistry

Abstract

References (26)

Adv. Organomet. Chem.

J. Organomet. Chem.

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Cited by (10)

Penta-arylcyclopentadienyl complexes

The preparation, crystal structure and some reaction chemistry of Bromo (η<sup>5</sup>-penta- phenylcyclopentadienyl) dicarbonylosmium (II) , [Os (η<sup>5</sup>-C<sup>5</sup>Ph<sup>5</sup>) (CO) <sup>2</sup>Br]

The molecular structure of organogermanium compounds

The crystal and molecular structure of (η<sup>5</sup>-pentaphenylcyclopentadienyl) (η<sup>5</sup>-cyclopentadienyl)iron(II), 1,2,3,4,5-pentaphenylferrocene, [Fe(C<inf>5</inf>Ph<inf>5</inf>)(C<inf>5</inf>H<inf>5</inf>)]

Bulky or Supracyclopentadienyl Derivatives in Organometallic Chemistry

Circumambulatory rearrangements of cyclopolyenes containing element-centred migrants