Synthesis and Characterization of [MnIII6(N-formylsalicylhydrazidate)6(MeOH)6]: A New Type of Macrocyclic Hexanuclear Manganese Cluster
详细信息 查看全文
- 作者：Byunghoon Kwak ; Hakjune Rhee ; Soonheum Park ; and Myoung Soo Lah
- 刊名：Inorganic Chemistry
- 出版年：1998
- 出版时间：July 13, 1998
- 年：1998
- 卷：37
- 期：14
- 页码：3599 - 3602
- 全文大小：74K
- 年卷期：v.37,no.14(July 13, 1998)
- ISSN：1520-510X
文摘
The macrocyclic hexanuclear metal cluster, [MnIII6(fshz)6S6], 1 (S = MeOH), was prepared using a trianionicpentadentate ligand, N-formylsalicylhydrazidate (fshz3-). Due to the meridional coordination of the ligand to themetal ion, the ligand is not only bridging the ring metal ions using a hydrazide N-N group but also enforcing thestereochemistry of the metal ions as a propeller configuration. The alternations of the chiralities of the metalcenters expand the cyclic ring system of complex 1 to the 24-membered ring system. The neutral hexanuclearmanganese complex with noncrystallographic pseudo-C3i symmetry is in the crystallographic inversion center.The disc-shaped hexanuclear cluster is 1.8 nm in diameter and 0.8 nm in thickness and has a vacant cavity in thecenter of the cluster. Three solvent molecules coordinated at the metal centers with 
configuration are in oneface of the cluster, and the remaining three solvent molecules coordinated at the other metal centers with 
configuration are in the other face of the cluster. The two faces of the cluster have opposite chiralities to eachother. The crystal packing structure of complex 1 shows that the disc-shaped hexanuclear clusters are alignedapproximately along the crystallographic a axis. The cavities of the clusters in the crystal structure are alsoaligned, and one-dimensional channels are formed. The solution integrity of the cluster was addressed usingsolution mass spectrometry, paramagnetically shifted 1H NMR spectroscopy, and UV-visible spectroscopy.Crystallographic data for 1: triclinic, P
, a = 10.0237(9) Å, b = 15.096(1) Å, c = 15.617(1) Å, 
= 112.142(5)
, 
= 106.615(5), 
= 99.958(7), V = 1989.8(3) Å3, Z = 2, Dcalcd = 1.510 g cm-1, R1 = 0.0502 and wR2= 0.1424 for 4249 reflections with I > 2
(I), GOF = 1.065.
configuration are in oneface of the cluster, and the remaining three solvent molecules coordinated at the other metal centers with configuration are in the other face of the cluster. The two faces of the cluster have opposite chiralities to eachother. The crystal packing structure of complex 1 shows that the disc-shaped hexanuclear clusters are alignedapproximately along the crystallographic a axis. The cavities of the clusters in the crystal structure are alsoaligned, and one-dimensional channels are formed. The solution integrity of the cluster was addressed usingsolution mass spectrometry, paramagnetically shifted 1H NMR spectroscopy, and UV-visible spectroscopy.Crystallographic data for 1: triclinic, P, a = 10.0237(9) Å, b = 15.096(1) Å, c = 15.617(1) Å, = 112.142(5), = 106.615(5), = 99.958(7), V = 1989.8(3) Å3, Z = 2, Dcalcd = 1.510 g cm-1, R1 = 0.0502 and wR2= 0.1424 for 4249 reflections with I > 2(I), GOF = 1.065.