High-Valent Organomanganese Chemistry. 1. Synthesis and Characterization of Manganese(III) and -(IV) Alkyls

Robert J. Morris, Gregory S Girolami

Research output: Contribution to journalArticle

Abstract

A new manganese(IV) alkyl, the hexamethylmanganate salt [Li(tmed)]2[MnMe6], has been prepared by treatment of MnMe4(PMe3)2 with methyllithium followed by addition of N,N,N′,N′-tetramethyl-ethylenediamine (tmed). The X-ray structure of the hexamethyl complex reveals an octahedral geometry for this d3 ion with the lithium atoms capping opposite faces in an asymmetric fashion: Mn-C = 2.12 (1) Å, Li-C = 2.20 (1), 2.35 (2), 2.53 (2) Å. Addition of excess methyllithium to Mn(acac)3 followed by treatment with tmed gives the pentamethylmanganate [Li(tmed)]2[MnMe5]. This trivalent species can also be obtained by a comproportionation reaction of the manganese(IV) complex [Li(tmed)]2[MnMe6] with 1 equiv of the manganese(II) complex [Li(tmed)]2[MnMe4] in diethyl ether. Interestingly, conducting the same comproportionation reaction in toluene leads to a different trivalent product, the tetramethylmanganate [Li(tmed)2][MnMe4]. The X-ray crystal structure of [Li(tmed)2] [MnMe4] reveals a square-planar geometry about manganese that is slightly distorted tetrahedrally: Mn-C = 2.078 (5) Å, C-Mn-C(trans) = 161.3 (2)°, C-Mn-C(cis) = 91.5 (2)°. Crystal data (Mo Kα, λ = 0.71073 Å): [Li(tmed)l2[MnMe6], space group Pbca, with a = 12.386 (4) Å, b = 13.358 (7) Å, c = 15.349 (7) Å, V = 2540 (4) Å3, Z = 4, T = 173 K, RF = 0.051, and RwF = 0.058 for 115 variables and 909 data; [Li(tmed)2][MnMe4], space group P21/n, with a = 9.818 (2) Å, b = 15.573 (2) Å, c = 15.245 (9) Å, β = 98.24 (4)°, V = 2307 (3) Å3, Z = 4, T = 198 K, RF = 0.044, and RwF = 0.044 for 321 variables and 2491 data. The nonexistence of the quadruply bonded dimanganese(III) complex [Mn2Me82−] is also discussed.

Original languageEnglish (US)
Pages (from-to)792-799
Number of pages8
JournalOrganometallics
Volume10
Issue number3
DOIs
StatePublished - Mar 27 1991

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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