1997
DOI: 10.1021/om9708337
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Abstract: The title lead(II) derivative was obtained as dark blue crystals by treatment of PbCl2 with (TMEDA = N,N,N‘,N‘-tetramethylethylenediamine) in tetrahydrofuran and its structure determined by X-ray diffraction. The compound is in effect the first dialkylead(II) species to be structurally characterized. The C−Pb−C angle is 117.1(2)°. Analogous treatment of SnCl2 yielded a yellow solid, which was judged from spectroscopic data to be the TMEDA complex of the analogous stannacycloalkane.

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Cited by 56 publications
(60 citation statements)
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“…In the solid state, the thus formed plumbylene dimer 82 exhibits a short leadϪ lead separation of 337.0(1) pm and a trans-bent angle of 46.5°. [76] However, the observed leadϪlead separations in In contrast, the not too dissimilar cyclic plumbylene 82, and especially in 81, are still markedly larger than the 75 [73] and the disilyl compound 74 [51] are strictly mono-bond length of 295Ϫ300 pm calculated for the parent commeric. The same holds for the diarylplumbylene 76, which pound H 2 PbϭPbH 2 .…”
Section: The Elusive Diplumbenesmentioning
confidence: 99%
“…In the solid state, the thus formed plumbylene dimer 82 exhibits a short leadϪ lead separation of 337.0(1) pm and a trans-bent angle of 46.5°. [76] However, the observed leadϪlead separations in In contrast, the not too dissimilar cyclic plumbylene 82, and especially in 81, are still markedly larger than the 75 [73] and the disilyl compound 74 [51] are strictly mono-bond length of 295Ϫ300 pm calculated for the parent commeric. The same holds for the diarylplumbylene 76, which pound H 2 PbϭPbH 2 .…”
Section: The Elusive Diplumbenesmentioning
confidence: 99%
“…[20] The barrier of 64.8 kcal mol À1 is approximately 20 kcal mol À1 above that calculated for the [3,3] rearrangement. [4] The total RHF/6-31G**//MP2/6-31G** Mulliken charges on the formates increase from approximately À 0.4 in the ground state molecules to À 0.6 in the transition states. No!…”
Section: David M Birney* Xiaolian Xu and Sihyun Hammentioning
confidence: 99%
“…The unique characteristics of these ªpseudopericyclicº reactions [2] have been described in detail elsewhere; [3] they can be briefly summarized as follows: 1) These reactions have planar transition states, 2) they may have very low barriers if the bond may be due in part to the relativistic contraction of the 6s electron pairs, which are only available for bond formation to a limited extent. [4] Recent ab initio [5] and density functional theory (DFT) calculations [6] found a chair and a flattened boat transition state for this reaction. geometries and the nucleophilic/electrophilic sites are favorable, and 3) no pseudopericyclic reaction can be forbidden by orbital symmetry.…”
Section: David M Birney* Xiaolian Xu and Sihyun Hammentioning
confidence: 99%
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“…The Pb-C bond length (7)1 is one of the widest among stable plumbylenes (ref. [4][5][6][7][8][9][10][11] and much wider than that theoretically predicted for dimethylplumbylene [93.01 owing to the steric repulsion of two bulky T'bt groups. The longer Pb-C bond lengths of plumbylene 9a compared with those of usual tetravalent organolead compounds are attributable not only to the steric repulsion between the substituents on the lead atom but also to the .…”
Section: Introductionmentioning
confidence: 96%