Chemistry of Molybdenum and Tungsten Bis[hydrazido(2−)] Complexes. Preparations and X-ray Crystal Structures of [Mo(NNMePh)2(S2CNMe2)2], [Mo(NNPh2)2(S2CNMe2)2]·Me2CO, [MoCl(NNMe2)2(PPh3)2]BPh4·CH2Cl2, and [Mo(NNMe2)2(bpy)2][BPh4]2·CH2Cl2

Joseph Chatt, Brian A.L. Crichton, Jonathan R. Dilworth, Phillip Dahlstrom, Robert Gutkoska, Jon Zubieta, Joseph Chatt, Brian A.L. Crichton, Jonathan R. Dilworth, Phillip Dahlstrom, Robert Gutkoska, Jon Zubieta

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Abstract

Complexes of the type [Mo(NNR2)2(S2CNR2)2] [R = MePh, Ph2; R2 = Me2, Et2, Ph2, (CH2)5] were prepared from [MoO2(S2CNR2)2] and R2NNH2. The structures of two derivatives were determined by X-ray diffraction. Crystal data: for R2 = Ph2 and R2 = Me2, space group P2/a, a = 17.054 (3) Å, b = 12.463 (2) Å, c = 14.030 (4) Å, β = 141.57 (7)°, V = 1853.34 Å3, Z = 2, R = 0.074 from 2905 reflections; for R2 = MePh and R2 = Me2, space group A2/a, a = 10.563 Å, b = 16.990 Å, c = 14.269 Å, β = 87.78 (8)°, V= 2558.9 λ3, Z = 4, R = 0.083 from 1732 reflections. Both are pseudooctahedral with nearly linear cis hydrazido(2−) ligands. The complexes [MCl(NNMe2)2(PR3)2]Cl (M = Mo, W, PR3 = PPh3, PPh2Me, PMe2Ph) were prepared from [MCl4(PR3)2] and Me3SiNHNMe2 in CH3CN. The structure of the complex with M = Mo, PR3 = PPh3 was determined by X-ray diffraction. Crystal data: monoclinic space group, P21/n, a = 20.996 (2) Å, b = 17.719 (5) Å, c = 16.409 (3) Å, β = 93.16 (1)°, V = 6095.1 (3) λ3, Z = 4, R = 0.046 from 4938 reflections. The cation is trigonal bipyramidal with apical PPh3 groups and the hydrazido groups in the equatorial plane. The complex with M = Mo, PR3 = PPh3 reacts with bipyridyl to give [Mo(NNMe2)2(bpy)2]2+ The structure of the bis(tetraphenylborate) salt was determined by X-ray diffraction: space group P21/c, a = 13.487 (3) Å, b = 13.875 (3) Å, c = 35.133 (5) Å, β = 100.18 (1) Å, V = 6471.00 Å3, Z = 4, R = 0.069 from 4253 reflections. The cation is pseudooctahedral again with nearly linear cis hydrazido groups.

Original languageEnglish (US)
Pages (from-to)2383-2391
Number of pages9
JournalInorganic Chemistry
Volume21
Issue number6
DOIs
StatePublished - Jan 1 1982
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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