η³-Allyl Coordination at Pb(II)

Abstract

Allylmagnesium chloride and methyl-propenyl-magnesium bromide were reacted with bulky substituted organolead and organotin halides (Ar*PbBr)2, (Ar′PbBr)2, (Ar*SnCl)2 (Ar* = 2,6-trip2C6H3-, trip = 2,4,6-triisopropylphenyl, Ar′ = 2,6-mes2C6H3-, mes = 2,4,6-trimethylphenyl). The allyl ligand coordinates in an η3-coordination mode at organoplumbylene fragments. In the solid state as well as in solution, η3-coordination was characterized by crystal structure analysis and Saunders’ isotopic perturbation technique. For the plumbylene Ar*Pb­(C3H5), a solid state 207Pb magic angle spinning (MAS) NMR spectrum could be obtained. The isotropic chemical shift is −435 ppm, and the magnitude of the 207Pb chemical shift tensor of 7000­(500) ppm is among the greatest observed experimentally. The methylallyl ligand coordinated at a plumbylene fragment exhibits two short and one long Pb–C interaction. In reaction with aniline, the allyl ligand reacts as a leaving group to give amidoplumbylenes.

Isolation and Computational Studies of a Series of Terphenyl Substituted Diplumbynes with Ligand Dependent Lead–Lead Multiple-Bonding Character

“…The terphenyl lead­(II) bromide precursors 2 – 4 were synthesized following established procedures ,, by addition of a diethyl ether solution of the terphenyl lithium salt to a diethyl ether suspension of PbBr 2 . During the preparation of 4 , the reaction mixture assumed a dark green color, likely due to some formation of the diarylplumbylene Pb­(Ar Pr i 4 -4-SiMe 3 ) 2 .…”

Effect of the Lead(II) Bond Angle on the Reactivity of Diaminoplumbylenes toward Ammonia: From Inertness to Immediate Ammonolysis

“…The plumbylenes of our study which undergo ammonolysis also react readily with aniline, affording the corresponding silylamine and the tetrameric lead imide [Pb­(NPh)] 4 (see the Supporting Information), which had been obtained before by Power from the reaction of PbCl 2 with [Mg­(NPh)­(THF)] 6 but had not been structurally characterized . We note that very recently Wesemann reported the reaction of the plumbylenes Ar*Pb­(η 3 -C 3 H 5 ) and Ar’Pb­(η 3 -C 3 H 5 ) (Ar’ = C 6 H 3 -2,6-Mes 2 , Mes = mesityl) with aniline, respectively affording Ar*Pb­(NHPh) and [Ar′Pb­(NHPh)] 2 . Like [Pb­(μ-NH 2 )­{nap­(NSiMe 3 )­(NHSiMe 3 )}] 2 and [Pb­(μ-NH 2 ) 2 Ar*] 2 , the latter plumbylene is dimeric.…”

“…23 We note that very recently Wesemann reported the reaction of the plumbylenes Ar*Pb(η 3 -C 3 H 5 ) and Ar'Pb(η 3 -C 3 H 5 ) (Ar' = C 6 H 3 -2,6-Mes 2 , Mes = mesityl) with aniline, respectively affording Ar*Pb(NHPh) and [Ar′Pb(NHPh)] 2 . 24 Like [Pb(μ-NH 2 ){nap(NSiMe 3 )(NHSiMe 3 )}] 2 and [Pb(μ-NH 2 ) 2 Ar*] 2 , the latter plumbylene is dimeric. In comparison with the planar Pb 2 N 2 core of [Pb(μ-NH 2 ){nap(NSiMe 3 )-(NHSiMe 3 )}] 2 , the Pb 2 N 2 moiety of [Ar′Pb(NHPh)] 2 is puckered with a dihedral angle between the two PbN 2 planes of 24.3°and exhibits ca.…”

Deprotonation of Organogermanium and Organotin Trihydrides

“…All solvents were subsequently degassed by 3× freeze/pump/thaw. [2,6-Trip 2 C 6 H 3 SnH 3 ], [2,6-Mes 2 C 6 H 3 SnH 3 ], [2,6-Trip 2 C 6 H 3 GeH 3 ], [2,6-Mes 2 C 6 H 3 SnCl] 2 , [2,6-Trip 2 C 6 H 3 SnCl] 2 , [2,6-Trip 2 C 6 H 3 SnH] 2 , [2,6-Trip 2 C 6 H 3 GeCl] 2 ,[2,6-Trip 2 C 6 H 3 PbBr] 2 , [2,6-Mes 2 C 6 H 3 PbBr] 2 , and [2,6-Trip 2 C 6 H 3 PbH] 2 were synthesized following literature procedures. ,,,,− Further chemicals were purchased commercially and used as received. Elemental analyses were performed at the Institute of Inorganic Chemistry, University of Tübingen using a Vario MICRO EL analyzer.…”