Publication Date:
2012-04-15
Description:
The synthesis of the trans -hyponitrite compounds Ph 3 E (μ-ONNO) E Ph 3 [ E = Ge ( 1 ), Pb ( 2 )] as well as their crystal and molecular structure are reported. Compound 1 crystallized from toluene/pentane in the trigonal space group R with a = 29.7969(18), b = 29.7969(18), c = 11.8465(6) Å; γ = 120°; V = 9108.8(9) Å 3 ; Z = 12, ρ = 1.461 g · cm –3 , T = 173(2) K. Compound 2 crystallized from toluene/ iso -hexane in the triclinic space group P with a = 10.0330(2), b = 11.0615(2), c = 24.2080(4) Å; α = 97.3730(10), β = 95.8550(10), γ = 115.3940(10)°; V = 2369.69(7) Å 3 ; Z = 3, ρ = 1.970 g · cm –3 , T = 173(2) K.The crystal structure determination revealed that two conformational isomers exist in the row of related group 14 element compounds. Whereas the species of tin and lead exhibit a S-shaped arrangement of the hyponitrite group between the two EPh 3 fragments, the corresponding germanium compound shows instead of a N-shape within the hyponitrite group. DFT calculations revealed that S-shaped conformers should be in all three cases the more stable ones. This stands in contrast to the observed N conformation of 1 in the crystal.
Print ISSN:
0044-2313
Electronic ISSN:
1521-3749
Topics:
Chemistry and Pharmacology
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