How Short is a -Ga⋮Ga- Triple Bond? Synthesis and Molecular Structure of Na2[Mes*2C6H3-Ga⋮Ga-C6H3Mes*2] (Mes* = 2,4,6-i-Pr3C6H2):  The First Gallyne

Author:

Su Jianrui1,Li Xiao-Wang1,Crittendon R. Chad1,Robinson Gregory H.1

Affiliation:

1. Department of Chemistry, The University of Georgia Athens, Georgia 30602-2556

Publisher

American Chemical Society (ACS)

Subject

Colloid and Surface Chemistry,Biochemistry,General Chemistry,Catalysis

Reference21 articles.

1. (a) Synthesis of Na2[Mes*2C6H3-Ga⋮Ga-C6H3Mes*2]:  Inside the drybox (M Braun Labmaster 130) a reaction vessel was charged with Mes*2C6H3GaCl21b(4.9 mmol), diethyl ether (25 mL), and finely cut sodium metal (43 mmol). Upon returning to the bench top, the system was allowed to stir (at room temperature) undisturbed for 2 weeks. Although the mixture initially turned green, it ultimately took on a dark brown color. An intensely dark red color was observed upon allowing the reaction vessel to stand undisturbed for 2 hours. Filtration and cooling to −20 °C for 1 week resulted in deposition of a multitude of dark red (almost black) crystals along the walls of the flask (1.62 g, 27% yield):  mp 188 °C. The crystalline compound contains one molecule of diethyl ether per asymmetric unit. Anal. (E + R Microanalytical Laboratories, Corona, NY). Calcd (Found) for C76H108Ga2Na2O:  C, 74.63 (73.68); H, 8.90 (8.90).1H NMR (300 MHz, 297 K, C2D5OC2D5):  δ 0.90 (m, 6H,CH3(ether)), 3.25 (q, 4H,CH2- (ether)), 0.81 (d, 12H,CH3(i-Pr)), 0.95 (d, 12H,CH3(i-Pr)), 1.00 (d, 12H,CH3(i-Pr)), 1.13 (d, 12H,CH3(i-Pr)), 1.18 (d, 12H,CH3(i-Pr)), 1.34 (d, 12H,CH3(i-Pr)), 2.73 (m, 12H,CH(i-Pr)), 6.54−7.28 (m, 6H,CH(aromatic)), 6.86 (s, 4H,CH(aromatic)), 6.92 (s, 4H,CH(aromatic)).13C NMR (300 MHz, 297 K, C2D5OC2D5):  δ 24.69, 30.57, 31.00, 31.13, 34.85, 35.31 (carbon atoms ofi-Pr), 120.3, 120.9, 127.0, 128.3, 128.6, 147.1, 147.3, 148.7 (aromatic carbon atoms). IR (Nujol mull):  718 s, 802 s, 873 s, 939 w, 1014 m, 1169 w, 1258 m, 1315 m, 1568 m, 1606 s.

2. Synthese und Molekülstruktur des Tetrakis[bis(trimethylsilyl)methyl]digallans(4) mit GalliumGallium-Bindung

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