Syntheses and structures of quinuclidine-stabilized four- and five-coordinate mono- and di-chlorogallane

Abstract

Hydride/chloride redistribution reactions provided high yields of GaCl₂H(quin) I, GaCl₂H(quin)₂ II, GaClH₂(quin) III and GaClH₂(quin)₂ IV(quin = quinuclidine) and structural characterization of compounds II and IV authenticate the unusual five-coordinate geometry for gallium hydride complexes.

References

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18. Compound III: mp: 89 °C, (decomp.). ¹H NMR (300 MHz, C₆D₆, 25 °C): δ0.82 (6H, m, CH₂), 1.04 (1H, m, CH), 2.49 (6H, t, NCH₂), 5.14 (2H, br s, GaH₂). Anal. Calc. for C₇H₁₅ClGaN: C, 38.50; H, 6.92; N, 6.41. Found: C, 38.27; H, 7.11; N, 6.30%.
19. Compound IV: MS (CI): 329.1 (11.8%, [(C₇H₁₃N)₂GaClH₃]⁺), 293.2 (15.7%, [(C₇H₁₃N)₂GaH₂]⁺), 216.0 (16.0%, [C₇H₁₃NGaClH₂]⁺), 182.0 (19.9%, C₇H₁₃NGaH₂]⁺), 112.1 (100%, [C₇H₁₃NH]⁺).
20. Crystal data: I: C₇H₁₄Cl₂GaN, M= 252.81, orthorhombic, space group Pbcm, a= 6.0102(2), b= 15.8808(3), c= 10.7925 (3)Å, V= 1030.11(5)ų , T= 173(2) K, Z= 4, µ= 3.132 mm^–1 , 6030 reflections collected, 962 independent reflections, 853 with I > 2σ(I), R₁= 0.0338, wR₂= 0.0802; IV: C₁₄H₂₈ClGaN₂, M= 329.56, orthorhombic, space group Pbcn, a= 10.9098(2), b= 12.0848(2), c= 12.3099(3)Å, V= 1622.97(6)ų, T= 173(2) K, Z= 4, µ= 1.847 mm^–1, 8527 reflections collected, 1433 independent reflections, 1202 with I > 2σ(I), R₁= 0.0296, wR₂= 0.0606; II: C₁₄H₂₃Cl₂GaN₂, M= 359.96, orthorhombic, space group Pmn2₁, a= 10.2217(6), b= 12.2916(7), c= 6.4620(4)Å, V= 811.89(8)ų, T= 173(2) K, Z= 2, µ= 2.013 mm^–1 , 4661 reflections collected, 1458 independent reflections, 1321 with I > 2σ(I), R₁= 0.0529, wR₂= 0.1365. CCDC 182/1093. See http://www.rsc.org/suppdata/cc/1999/123/ for crystallographic files in .cif format.
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22. Compound V: mp 239–245 °C. ¹H NMR (300 MHz, C₆D₆, 25 °C): δ 0.66 (m, 6H, CH₂), 0.89 (m, 1H, CH), 2.62 (t, 6H, NCH₂). Anal. Calc. for C₇H₁₃NGaCl₃: C, 29.27; H, 4.56; N, 4.88. Found: C, 29.48; H, 4.98; N, 4.81%.