Conformational Preferences Driven by the C-Methyl Substituent in Chelated o-Diphenylphosphino--methyl-N,N-dimet
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- 作者：M. Ará ; nzazu Alonso ; Juan A. Casares ; Pablo Espinet ; Katerina Soulantica ; A. Guy Orpen ; and Hirihattaya Phetmung
- 刊名：Inorganic Chemistry
- 出版年：2003
- 出版时间：June 16, 2003
- 年：2003
- 卷：42
- 期：12
- 页码：3856 - 3864
- 全文大小：158K
- 年卷期：v.42,no.12(June 16, 2003)
- ISSN：1520-510X
文摘
The stereochemistry of the chelate rings of a number of rhodium aminophosphine complexes is studied by NMRspectroscopy. The similarity in the variable-temperature behavior for the different compounds is consistent withthem having in common highly preferred chelate ring conformations. The six-membered metallacycle of coordinated(R)-P*N (P*N = o-diphenylphosphino-
-methyl-N,N-dimethylbenzylamine) adopts a 
conformation in the solidstate. NMR experiments indicate that this conformation is strongly favored in solution as well. The preferred senseof helicity is imposed by the absolute configuration of the stereogenic carbon atom on the ligand, which exerts animportant steric control. The complex [Rh(TFB){(C6H4CHMeNMe2)2P(C6H4CHMeNHMe2)}](BF4)2·H2O·Me2COcrystallizes in the monoclinic space group P2(1) with a = 12.0548(11) Å, b = 16.139(2) Å, c = 12.1804(10) Å,
= 100.742(9)
, Z = 4.
-methyl-N,N-dimethylbenzylamine) adopts a conformation in the solidstate. NMR experiments indicate that this conformation is strongly favored in solution as well. The preferred senseof helicity is imposed by the absolute configuration of the stereogenic carbon atom on the ligand, which exerts animportant steric control. The complex [Rh(TFB){(C6H4CHMeNMe2)2P(C6H4CHMeNHMe2)}](BF4)2·H2O·Me2COcrystallizes in the monoclinic space group P2(1) with a = 12.0548(11) Å, b = 16.139(2) Å, c = 12.1804(10) Å, = 100.742(9), Z = 4.