Metal-Metal Bonded Diruthenium(II, III) Assemblies with the Polycyano Anionic Linkers N(CN)2-, C(CN)3-, and 1,4-Dicyanamido-2,5-dimethylbenzene (DM-Dicyd
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- 作者：Hitoshi Miyasaka ; Rodolphe Clé ; rac ; Cristian S. Campos-Ferná ; ndez ; and Kim R. Dunbar
- 刊名：Inorganic Chemistry
- 出版年：2001
- 出版时间：March 26, 2001
- 年：2001
- 卷：40
- 期：7
- 页码：1663 - 1671
- 全文大小：143K
- 年卷期：v.40,no.7(March 26, 2001)
- ISSN：1520-510X
文摘
The new metal-metal bonded diruthenium(II,III) compounds [Ru2(O2CCH3)4(
-L)]
(L = N(CN)2-, 1; C(CN)3-,2) and [{Ru2(O2CCH3)2(mhp)2}2(-DM-Dicyd)] (3) (mhp = 2-oxy-6-methylpyridinate, DM-Dicyd = 1,4-dicyanamido-2,5-dimethylbenzene dianion) have been synthesized and fully characterized. Compounds 1 and 2were synthesized by the reaction of [Ru2(O2CCH3)4(NCCH3)2](BF4) with NaN(CN)2 and KC(CN)3, respectively.The "dimer-of-dimers", 3, was synthesized by a 2:1 reaction of [Ru2(O2CCH3)2(mhp)2(MeOH)](BF4) with[As(Ph)4]2[DM-Dicyd]. Compound 1 crystallizes in the monoclinic space group C2/m with a = 10.174(2) Å, b= 13.016(3) Å, c = 7.0750(14) Å, 
= 101.83(3)
, and Z = 2. Compound 2 crystallizes in the orthorhombicspace group Fdd2 with a = 29.679(6) Å, b = 31.409(6) Å, c = 7.3660(15) Å, V = 6866(2) Å3, and Z = 16. Incompound 1, dicyanamide anions (N(CN)2-) bridge the [Ru2(O2CCH3)4]+ units in an end-to-end bridging mode,thereby forming an alternating one-dimensional chain. In compound 2, two cyano groups of tricyanomethanideanion (C(CN)3-) are coordinated to independent [Ru2(O2CCH3)4]+ units to give a chain similar to that found in1. The Ru-Ru bond distances in 1 and 2 are 2.2788(14) and 2.2756(5) Å, respectively, which are typical valuesfor Ru2(O2CR)4Cl and [Ru2(O2CR)4]+ compounds. The Ru-N distances are 2.257(8) Å in 1 and 2.259(4) and2.283(4) Å in 2. The temperature dependence of the magnetic susceptibilities of compounds 1-3 reveals a weakantiferromagnetic interaction between Ru2 units (S = 3/2) through each polycyano anionic linker: g = 2.16, zJ =-0.33 cm-1, D = 63.3 cm-1 for 1; g = 2.15, zJ = -0.22 cm-1, D = 58.0 cm-1 for 2; and g = 2.10, zJ = -0.90cm-1, D = 75.0 cm-1 for 3.
-L)] (L = N(CN)2-, 1; C(CN)3-,2) and [{Ru2(O2CCH3)2(mhp)2}2(-DM-Dicyd)] (3) (mhp = 2-oxy-6-methylpyridinate, DM-Dicyd = 1,4-dicyanamido-2,5-dimethylbenzene dianion) have been synthesized and fully characterized. Compounds 1 and 2were synthesized by the reaction of [Ru2(O2CCH3)4(NCCH3)2](BF4) with NaN(CN)2 and KC(CN)3, respectively.The "dimer-of-dimers", 3, was synthesized by a 2:1 reaction of [Ru2(O2CCH3)2(mhp)2(MeOH)](BF4) with[As(Ph)4]2[DM-Dicyd]. Compound 1 crystallizes in the monoclinic space group C2/m with a = 10.174(2) Å, b= 13.016(3) Å, c = 7.0750(14) Å, = 101.83(3), and Z = 2. Compound 2 crystallizes in the orthorhombicspace group Fdd2 with a = 29.679(6) Å, b = 31.409(6) Å, c = 7.3660(15) Å, V = 6866(2) Å3, and Z = 16. Incompound 1, dicyanamide anions (N(CN)2-) bridge the [Ru2(O2CCH3)4]+ units in an end-to-end bridging mode,thereby forming an alternating one-dimensional chain. In compound 2, two cyano groups of tricyanomethanideanion (C(CN)3-) are coordinated to independent [Ru2(O2CCH3)4]+ units to give a chain similar to that found in1. The Ru-Ru bond distances in 1 and 2 are 2.2788(14) and 2.2756(5) Å, respectively, which are typical valuesfor Ru2(O2CR)4Cl and [Ru2(O2CR)4]+ compounds. The Ru-N distances are 2.257(8) Å in 1 and 2.259(4) and2.283(4) Å in 2. The temperature dependence of the magnetic susceptibilities of compounds 1-3 reveals a weakantiferromagnetic interaction between Ru2 units (S = 3/2) through each polycyano anionic linker: g = 2.16, zJ =-0.33 cm-1, D = 63.3 cm-1 for 1; g = 2.15, zJ = -0.22 cm-1, D = 58.0 cm-1 for 2; and g = 2.10, zJ = -0.90cm-1, D = 75.0 cm-1 for 3.