Übergangsmetallsubstituierte Gallane: Synthese, Struktur und Bindungsverhältnisse von [(CO)4CoGaEt2(NC7H13)], [(PMe3)(CO)3CoGaCl2(NMe3)], [(CO)4CoGaCl3]K und [(CO)5MnGaEt2(NC7H13)]

✍ Scribed by Roland A. Fischer; Alexander Miehr; Holger Hoffmann; Wolfram Rogge; Christian Boehme; Gernot Frenking; Eberhardt Herdtweck

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: German
• Weight: 238 KB
• Volume: 625
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/(sici)1521-3749(199909)625:9<1466::aid-zaac1466>3.0.co;2-o

✦ Synopsis

Inhaltsu È bersicht. Die u È bergangsmetallsubsituierten Gallane [(CO) 5 MnGaEt 2 (NC 7 H 13 )] (1), [(PMe 3 )(CO) 3 CoGaCl 2 (NMe 3 )] (2), [(CO) 4 CoGaEt 2 (NC 7 H 13 )] (3) und [(CO) 4 CoGaCl 3 ]K (4) wurden durch Reaktion der Carbonylmetallate [(CO) n M] (Na/K) mit den Galliumchloriden ClGaEt 2 (NC 7 H 13 ), Cl 3 Ga(NMe 3 ) bzw. GaCl 3 erhalten. Die Einkristallstrukturbestimmungen ergaben fu È r 1: Raumgruppe P2 1 /c (I.T.-Nr.: 14); Z = 4; a = 1425,4(2) pm, b = 1007,4(1) pm, c = 1429,9(3) pm; b = 113,92(1)°; 2: Raumgruppe P2 1 /m (I.T.-Nr.: 11); Z = 2; a = 746,1(1) pm, b = 1131,2(1) pm, c = 1061,5(1) pm; b = 101,87(1)°; 3: Raumgruppe P2 1 /c (I.T.-Nr.: 14); Z = 8; a = 1405,9(2) pm, b = 1786.2(2) pm, c = 1430,9(2) pm; b = 91,47(1)°; 4: Raumgruppe P2 1 /c; Z = 4; a = 1185,7(1) pm, b = 895,4(1) pm, c = 1144,7(3) pm; b = 106,47(2)°. Anhand der Modellverbindungen [{L'(CO) 3 Co}GaX 2 L] (L' = CO, PH 3 ; L = NH 3 , X = H, Cl) wurden die polaren r(Co±Ga)-Bindungen und die Substituenteneffekte auf die Bindungsla È nge auf der Basis quantenchemischer Dichtefunktionalrechnungen (DFT) charakterisiert. Transition Metal substituted Gallanes: Synthesis and X-Ray Structures of [(CO) 4 CoGaEt 2 (NC 7 H 13 )], [(PMe 3 )(CO) 3 CoGaCl 2 (NMe 3 )], [(CO) 4 CoGaCl 3 ]K, and [(CO) 5 MnGaEt 2 (NC 7 H 13 )] Abstract. The transition metal substituted gallanes [(CO) 5 MnGaEt 2 (NC 7 H 13 )] (1), [(PMe 3 )(CO) 3 CoGaCl 2 (NMe 3 )] (2), [(CO) 4 CoGaEt 2 (NC 7 H 13 )] (3), and [(CO) 4 CoGaCl 3 ]K (4) were obtained by the reaction of the potassium/sodium salts of the manganese-and cobaltcarbonylmetallates with the chlorogallium species ClGaEt 2 (NC 7 H 13 ), Cl 3 Ga(NMe 3 ), and GaCl 3 . The structures were established by single crystal X-ray analysis 1: space group P2 1 /c (I.T.-No.: 14); Z = 4; a = 1425.4(2) pm, b = 1007.4(1) pm, c = 1429.9(3) pm; b = 113.92(1)°; 2: space group P2 1 /m (I.T.-No.: 11); Z = 2; a = 746.1(1) pm, b = 1131.2(1) pm, c = 1061.5(1) pm; b = 101.87(1)°; 3: space group P2 1 /c (I.T.-No.: 14); Z = 8; a = 1405.9(2) pm, b = 1786.2(2) pm, c = 1430.9(2) pm; b = 91.47(1)°; 4: space group P2 1 /c; Z = 4; a = 1185.7(1) pm, b = 895.4(1) pm, c = 1144.7(3) pm; b = 106.47(2)°. The model compounds [{L'(CO) 3 Co}GaX 2 L] (L' = CO, PH 3 ; L = NH 3 , X = H, Cl) with polar r(Co±Ga) bonds and the effect of the substituent on the bond length are characterized with DFT-calculations.