The Chemistry of (Cyclopentadienyl)phenyl-lead(IV) Compounds

Article abstract of DOI:10.1039/DT9820001055

The yellow air-stable (cyclopentadienyl)phenyl-lead(IV) compounds, PbPh(4-n)(cp)n , have been synthesised by the reaction of the corresponding phenyl-lead(IV) chloride and lithium cyclopentadienide in diethyl ether.Crystals of PbPh3(cp) are monoclinic, space group P2₁/c, with a = 9.5426, b = 12.3843, c = 16.1714 Angstroem, β = 102.3358 degree, and Z = 4, and comprise discrete non-interacting molecules with a distorted tetrahedral geometry.The Pb-C(cp) bond distance <2.30(2) Angstroem> is significantly longer than the Pb-C(Ph) distances , indicating a substantial weakening of this bond.The endocyclic C-C bonds of the cyclopentadienyl ring (which is planar) are consistent with a concentration of ?-electron density over the carbon atoms remote from the lead.Reaction of PbPh3(cp) with acetic acid, thiophenol, and imidazole proceeds with exclusive Pb-C(cp) bond cleavage affording PbPh3(O2CMe), PbPh3(SPh), and PbPh3(N2C3H3), respectively.Only PbPh4 was isolated from the reaction with 4-chlorophenol.The compound PbPh2(cp)2 decomposes on attempted sublimation at 60-70 deg C and 0.01 mmHg giving Pb(cp)2, whilst reaction with hidrogen chloride, carboxylic acids, and imidazole yields the corresponding diphenyl-lead(IV) derivative.Cleavage of all four Pb-C bonds occurs on reaction with thiols, when lead(II) thiolates are the products.Reaction with phenols yields products of composition n which presumably contain metal-metal bonds.The mechanisms of the reactions are discussed.

Full text of DOI:10.1039/DT9820001055

View Article Online / Journal Homepage / Table of Contents for this issue

View Article Online

View Article Online

View Article Online

View Article Online

View Article Online