Syntheses, structures, and reactivities of heteroleptic magnesium amide thiolates

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The syntheses and characterizations of a family of novel heteroleptic magnesium amide thiolates are presented. The compounds are synthesized by ligand redistribution chemistry involving reactions of equimolar amounts of magnesium amides and magnesium thiolates. Utilization of the smaller thiolates [Mg(SPh)2](n) and [Mg(S-2,4,6-(i)Pr3C6H2)2](n) results in the isolation of dimeric species, [Mg(THF)(N(SiMe3)2)(μ-SR)]2 (R = Ph (1), 2,4,6-(i)Pr3C6H2 (2)), with four-coordinate metal centers and bridging thiolate functions. The sterically more encumbered thiolate S-2,4,6-(t)Bu3C6H2 induces the formation of the four-coordinate, monomeric species Mg(THF)2(N(SiMe3)2)(S-2,4,6-(t)Bu3C6H2) (3)). Careful choice of reaction conditions allows the successful syntheses of pure heteroleptic compounds; however, it remains difficult to obtain the compounds in high yields, since a tendency toward product symmetrization and ligand redistribution under re-formation of the starting materials is prevalent. One of these symmetrized products is also included in this report: the dimeric, four-coordinate magnesium thiolate [Mg(THF)(S-2,4,6-(t)Bu3C6H2)(μ-S-2,4,6-(t)Bu3C6H2)]2 (4), isolated as the product of the reaction between [Mg(N(SiMe3)2)2]2 and Mg(THF)2(S-2,4,6-(t)Bu3C6H2)2. All compounds were characterized by NMR and IR speclxoscopy, elemental analyses, and X-ray crystallography. Crystal data obtained with Mo Kα (λ = 0.710 73 Å) radiation are as follows. 1: C16H31MgNOSSi2, a = 11.2100(1) Å, b = 17.4512(3) Å, c = 11.2999(2) Å, β = 97.952(1)°, V = 2189.32(6) Å3, Z = 4, monoclinic, space group P21/n, R1 (all data) = 0.0934. 2: C25H49MgNOSSi2, a = 11.1691(1) Å, b = 11.0578(1) Å, c = 26.0671(4) Å, β = 99.906(1)°, V = 3171.44(6) Å3, Z = 4, monoclinic, space group P21/c, R1 (all data) = 0.0557. 3: C36H71MgNO3SSi2, a = 42.8293(16) Å, b = 10.9737(5) Å, c = 16.8305(7) Å, β = 98.755(3)°, V = 7818.1(6) Å3, Z = 8, monoclinic, space group C2/c, R1 (all data) = 0.1331. 4: C80H132Mg2O2S4, a = 18.8806(2) Å, b = 19.3850(2) Å, c = 27.3012(4) Å, β = 97.250(1)°, V = 9912.4(2) Å3, Z = 4, monoclinic, space group P21/n, R1 (all data) = 0.1023.

Original languageEnglish (US)
Pages (from-to)3875-3880
Number of pages6
JournalInorganic Chemistry
Issue number17
StatePublished - Aug 21 2000

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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