Tris(triphenylplumbyl)plumbate: an anion with three stretched lead–lead bonds

Abstract

Treatment of lead(II) bromide with phenylmagnesium bromide at low temperature furnishes yellow crystals of the ionic compound [BrMg(THF)5]+ [:Pb(PbPh3)3]- which, upon X-ray crystallographic analysis, reveals three stretched Pb-Pb bonds and Pb-Pb-Pb angles of about 93 degrees.

Monoanionic Tin Oligomers Featuring Sn–Sn or Sn–Pb Bonds: Synthesis and Characterization of a Tris(Triheteroarylstannyl)Stannate and -Plumbate

“…Accordingly, the Sn-Pb-Sn angles are relatively small with values ranging from 90.85(1)° to 94.49(1)°. Similar structural features can be found in the previously reported tris(plumbyl)plumbate anions, where angles around the central lead atom average to 93.0° [11] and 94.1° [12]. The Pb-Sn bond lengths amount to 2.8743(3) and 2.8919(4) Å, and may be compared with 2.7844(4) Å in Pb(Ar)SnAr3 (Ar = C6H3-2,6-(O i Pr)2) and 2.9283(4) Å in Pb(SnAr3)2 [26].…”

New Pb–Pb bonds: syntheses and molecular structures of hexabiphenyldiplumbane and tri(trisbiphenylplumbyl)plumbate

“…Could the considerable difference in the nature of reaction products 1 and 2 be traced to a neat THF solvent system versus a THF-1,4dioxane mixed solvent system? While the mechanism of formation of 2, as Weidenbruch suggested for [(THF) 5 MgBr][Pb(PbPh 3 ) 3 ], 11 remains unclear, we agree with these workers that reactions of lead(II) halides with Grignard reagents would appear to be more complicated than one would initially suspect.…”

“…Indeed, other than the tri(trisbiphenylplumbyl)plumbate anion 2 reported herein, the literature reveals only two other such species, both recently reported: (1) the novel hexaarylcyclotriplumbane containing a lead three-membered ring, [(i-Pr 3 C 6 H 2 ) 2 Pb] 3 ; 10 and (2) the closely related tris(triphenylplumbyl)plumbate anion, [Pb(PbPh 3 ) 3 ] 2 (cation: [(THF) 5 MgBr] 1 ). 11 The coordination of the central lead atom in both [Pb(PbPh 3 ) 3 ] 2 and 2 (Fig. 2) may be described as trigonal pyramidal with the lone pair of electrons residing at the apex.…”

Complications in metathesis reactions involving Grignard reagents: Effect of solvent on products obtained from the interaction of PhMgBr with GaCl3 or InBr3

“…[MgBr(THF) 5 ] + , while in compound 5, the asymmetric unit is comprised of half the [Mg(THF) 6 ] 2+ cation and one anion. The cation in 4 represents a rare example of the [MgBr(THF) 5 ] + species, and interestingly, the three other structurally authenticated instances of this ion were all also derived from Grignard reagents [18][19][20]. The bond lengths and angles are given in the captions for Figs.…”