Synthesis and Structure of Unassociated Mono-, Di-, and Trithiolate Derivatives of Aluminum and Gallium: Investigation of Al-S and Ga-S π-Bonding

Rudolf J. Wehmschulte, Karin Ruhlandt-Senge, Philip P. Power

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38 Scopus citations

Abstract

The synthesis and characterization of several sterically crowded aluminum and gallium thiolates are described. The major reason for these studies was the investigation of the possible occurrence of π-bonding in Al-S and Ga-S bonds and the determination of the steric requirements for the isolation of monomeric heavier main group 3 thiolates in the solid state. The compounds examined were RAl(SMes*)2 (R = n-Bu, 1; t-Bu, 2), Mes*2GaSR (Mes* = 2,4,6-t-Bu3C6H2, R = Me, 3; Ph, 4), n-BuGa(SMes*)2, (5) (t-Bu2AlSTrip)2 (6) (Trip = 2,4,6-i-Pr3C6H2), (THF)Al(STrip)3 (7). They were characterized by X-ray crystallography (1–3, 5–7) and by NMR and IR spectroscopy. The data indicate that the M-S, p-p, π-bonding is weak and has an upper limit of 8–9 kcal mol−1. Restricted rotation around an M-S bond was detected only in the cases of Mes*2GaSMe (3) and Mes*2-GaSPh (4). Crystal data at 130 K with Mo Kα (λ = 0.710 69 Å) (2, 5–7) or Cu Kα (λ = 1.541 78 Å) (1, 3) radiation; 1, n-BuAl(SMes*)2, C40H67AlS2, a = 18.563(5) Å, b = 27.171(11) Å, c = 32.089(4) Å, orthorhombic, Z = 16 (two independent molecules), space group Pbca, R = 0.087 for 6746 (I > 2σ(I)) data; 2, t-BuAl(SMes*)2, C40H67AlS2, a = 17.375(9) Å, b = 27.982(10) Å, c = 17.868(8) Å, β = 112.29(2)°, Z = 8 (two independent molecules), monoclinic, space group P21/c, R = 0.082 for 8425 (I > 2σ(I)) reflections; 3, Mes*2GaSMe, C37H61-GaS, a = 33.654(8) Å, b = 10.433(4) Å,c = 20.258(8) Å, Z = 8, orthorhombic, space group Pbcn, R = 0.066 for 3164 (I > 2σ(I)) reflections; 5, n-BuGa(SMes*)2, C40H67GaS2, a = 18.521(8) Å, b = 27.342(10) Å, c = 32.046(12) Å, orthorhombic, Z = 16 (two independent molecules), space group Pbca, R = 0.144 for 3297 (I > 2σ(I)) reflections; 6, (t-Bu2AlSTrip)2, C46H82A12S2, a = 20.820(8) Å,b= 14.598(6) Å, c = 16.118(4) Å, Z = 4, orthorhombic, space group Pna21 R = 0.062 for 2469 (I > 2.5σ(I)) data; 7, (THF)Al(STrip)3-0.5C6H14, C52H84-AlOS3, a = 15.589(6) Å,b= 13.622(5) Å, c = 26.308(12) Å, β = 99.88(2)°, Z = 4, monoclinic, space group P21/c, R = 0.075 for 5697 (I > 3σ(I)) data.

Original languageEnglish (US)
Pages (from-to)2593-2599
Number of pages7
JournalInorganic Chemistry
Volume34
Issue number10
DOIs
StatePublished - May 1 1995
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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