A New Bridging Ligand for the [Mo2]4+ Dimer: Syntheses and X-ray Crystal Structures of the Redox Pair [Mo2{
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- 作者：Philip J. Bailey ; Simon F. Bone ; Lindsey A. Mitchell ; Simon Parsons ; Kenneth J. Taylor ; and Lesley J. Yellowlees
- 刊名：Inorganic Chemistry
- 出版年：1997
- 出版时间：February 26, 1997
- 年：1997
- 卷：36
- 期：5
- 页码：867 - 871
- 全文大小：190K
- 年卷期：v.36,no.5(February 26, 1997)
- ISSN：1520-510X
文摘
The quadruply bonded molybdenum dimer[Mo2{
-
2-(NPh)2CNHPh}4](1), bridged by four triphenylguanidineanion (guanidino) ligands, has been synthesized and structurallycharacterized. The guanidino ligands greatlystabilize the oxidized forms of this complex, and it is reversiblyoxidized to the red monocation and the bluedication at readily accessible potentials(E1/2 = -0.05 and +0.85 V vsAg/AgCl, respectively). The [Mo2{-2-(NPh)2CNHPh}4]+cation (2) has also been structurally characterized as its[BF4]- salt showing that theMo-Mo distance increases from 2.0839(9) to 2.2902(12) Å onoxidation, an unprecedented increase for such systemsand almost 4 times that previously observed for a[Mo2]4+/5+ pair. TheN-Mo-Mo-N torsion angle is alsofound to increase from 4.5 to 7.6
on oxidation. Thecrystallographic data are as follows.1·2.2Et2O:C84.8H86Mo2N12O2.2, monoclinic,P2/n, a = 13.127(3) Å,b = 14.335(3) Å, c = 22.752(3) Å,
= 90.434(13), Z = 2.2[BF4]-·3CH2Cl2:C79H70BCl6F4Mo2N12,monoclinic, P21/c, a=13.426(3) Å, b = 23.693(7) Å,c = 23.573(7)Å, = 92.93(2), Z = 4.
-2-(NPh)2CNHPh}4](1), bridged by four triphenylguanidineanion (guanidino) ligands, has been synthesized and structurallycharacterized. The guanidino ligands greatlystabilize the oxidized forms of this complex, and it is reversiblyoxidized to the red monocation and the bluedication at readily accessible potentials(E1/2 = -0.05 and +0.85 V vsAg/AgCl, respectively). The [Mo2{-2-(NPh)2CNHPh}4]+cation (2) has also been structurally characterized as its[BF4]- salt showing that theMo-Mo distance increases from 2.0839(9) to 2.2902(12) Å onoxidation, an unprecedented increase for such systemsand almost 4 times that previously observed for a[Mo2]4+/5+ pair. TheN-Mo-Mo-N torsion angle is alsofound to increase from 4.5 to 7.6 on oxidation. Thecrystallographic data are as follows.1·2.2Et2O:C84.8H86Mo2N12O2.2, monoclinic,P2/n, a = 13.127(3) Å,b = 14.335(3) Å, c = 22.752(3) Å, = 90.434(13), Z = 2.2[BF4]-·3CH2Cl2:C79H70BCl6F4Mo2N12,monoclinic, P21/c, a=13.426(3) Å, b = 23.693(7) Å,c = 23.573(7)Å, = 92.93(2), Z = 4.