An Unusual Transition Metal Cluster Containing a Seven Metal Atom Plane. Syntheses and Crystal Structures of [Mn][Mn7(THF)6(CO)12]2, Mn3(THF)2(CO)10, and [Mn(THF)6][Mn(CO)5]2

Gapgoung Kong, George N. Harakas, Bruce R. Whittlesey

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Abstract

Dimanganese decacarbonyl reacts with trimethylaluminum in a mixture of hexane and tetrahydrofuran to produce [Mn][Mn7(THF)6(CO)12]2(1; THF = tetrahydrofuran) and the unstable compounds Mn3(THF)2(CO)10(2) and [Mn(THF)6][Mn(CO)5]2 (3). The crystal structure of 1 is made up of two Mn7(THF)6(CO)12- anions, each of which is coordinated to an isolated Mn2+ cation via three carbonyl oxygens to give an octahedral coordination geometry about the cation. The framework of each Mn7(THF)6(CO)12- anion consists of a ring of six manganese atoms, all of which are attached to a seventh manganese in the center of the ring to form a planar Mn7 unit. The six-membered ring is made up of alternating Mn(CO)4 and Mn(THF)2 groups, and if metal—metal bonds to the central manganese are ignored, the former have approximate octahedral coordination while the latter have somewhat distorted tetrahedral geometries. The complex crystallizes in two forms, one form that contains two molecules per formula unit of the tetrahydrofuran adduct of trimethylaluminum, and another form in which the trimethylaluminum adduct is absent. Crystal data for [Mn][Mn7(THF)6(CO)12]2•2Al(CH3)3THF: monoclinic space group P21/c (No. 14), a = 13.630(3) Å, b = 24.847(5) Å, c = 17.645(4) Å, β = 106.01(3)°, Z = 2, R = 6.56%, Rw = 6.75%. Crystal data for [Mn][Mn7(THF)6(CO)12]2: monoclinic space group P21/c (No. 14), a = 18.268(2) Å, b = 20.395(4) Å, c = 15.143(2) Å, β= 103.064(8)°, Z = 2, R = 8.75%, Rw = 9.55%. The structure of 2 consists of two Mn(CO)5 groups connected by metal—metal bonds to a central Mn(THF)2unit, and 3 consists of isolated [Mn(THF)6]2+ and [Mn(CO)5]- ions. Crystal data for Mn3(THF)2(CO)10 (2): monoclinic space group P21/n (No. 14), a = 8.9394(7) Å, b = 16.795(2) Å, c = 16.048(2) Å, β= 95.239(8)°, Z = 4, R = 4.26%, Rw = 3.85%. Crystal data for [Mn(THF)6][Mn(CO)5]2(3): triclinic space group P1 (No. 2), a = 10.352(1) Å, b = 10.443(1) Å, c = 19.552(3) Å, α = 83.86(1)°, β = 88.14(1)°, γ = 86.037(9)°, Z = 2, R = 6.57%, Rw= 9.07%.

Original languageEnglish
Pages (from-to)3502-3509
Number of pages8
JournalJournal of the American Chemical Society
Volume117
Issue number12
DOIs
StatePublished - Mar 1995

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