Syntheses and X-ray Structures of a Series of Chalcogen-Containing Manganese Carbonylates [E(2)Mn(3)(CO)(9)](-), [E(8)C(2)Mn(2)(CO)(6)](2-), and [E(2)Mn(4)(CO)(12)](2-) (E = Se, S).
The reaction of SeO(2) with Mn(2)(CO)(10)/KOH in methanol solution forms a trigonal bipyramid cluster anion [Se(2)Mn(3)(CO)(9)](-) (Ia). Cluster Ia can also be synthesized from the treatment of Se powder with Mn(2)(CO)(10)/KOH in 2:1 molar ratio in methanol solution. If Se is reacted with Mn(2)(CO)(10)/KOH in a molar ratio of 8:1, the deoxygenation occurs to produce a novel cluster [Se(8)C(2)Mn(2)(CO)(6)](2)(-) (IIa). Cluster IIa can readily transform into a new octahedral cluster [Se(2)Mn(4)(CO)(12)](2)(-) (IIIa) by further treatment with Mn(2)(CO)(10)/KOH in CH(2)Cl(2)/MeOH solutions, and the use of a molar ratio of 1:1 of Se powder to Mn(2)(CO)(10)/KOH in methanol also can yield complex IIIa. In the sulfur-manganese system, the synthesis of the analogous complexes [S(2)Mn(3)(CO)(9)](-) (Ib), [S(8)C(2)Mn(2)(CO)(6)](2)(-) (IIb), and [S(2)Mn(4)(CO)(12)](2)(-) (IIIb) also can be accomplished from the reactions of S powder with Mn(2)(CO)(10)/KOH in similar fashions. Clusters Ia-IIIa and Ib-IIIb are fully characterized by spectroscopic methods or/and X-ray analyses. The novel clusters [E(8)C(2)Mn(2)(CO)(6)](2)(-) (E = Se, IIa; E = S, IIb) each consist of two separate Mn(CO)(3) groups which are doubly bridged by two CE(4) fragments. Clusters Ia and Ib each display a trigonal bipyramid framework with two chalcogen atoms in the axial positions, while clusters IIIa and IIIb each exhibit an octahedral metal skeleton.
Huang
Kuo-Chih
KC
Department of Chemistry, National Taiwan Normal University, Taipei 11718, Taiwan, Republic of China, and Instrumentation Center and Department of Chemistry, National Taiwan University, Taipei 10764, Taiwan, Republic of China.
Tsai
Yi-Chou
YC
Lee
Gene-Hsiang
GH
Peng
Shie-Ming
SM
Shieh
Minghuey
M