TY - JOUR
T1 - Sodium and Potassium Triisopropylbenzenethiolates
T2 - Influence on Solid-State Structure by Metal and Donor
AU - Englich, Ulrich
AU - Chadwick, Scott
AU - Ruhlandt-Senge, Karin
PY - 1998
Y1 - 1998
N2 - The synthesis and characterization of a family of sodium and potassium thiolates [A(donor)S(Trip)]2 (A = Na, K; Trip = 2,4,6-i-Pr3C6H2, n = 1-∞) is described. [Na(PMDTA)S(Trip)]2, 1 (PMDTA = N,N,N′,N″,N″-pentamethyldiethylenetriamine), [(NaS(Trip))2(Na(Et2O)S(Trip))4]·0.5 solvent, 2, [Na(TMEDA)S(Trip)]infin;, 3 (TMEDA = N,N,N′,N′-tetramethylethylenediamine), [Na(THF)S(Trip)]n, 4 (n = 6 or ∞), [K(dibenzo-18-crown-6)(THF)S(Trip)]·THF, 5, [(KS(Trip))2(K(THF)S(Trip))2(K(THF) 2S(Trip))2], 6, [K(THF)S(Trip)]infin;, 7, [(K(THF)S(Trip))2(K(TMEDA)S(Trip))2(KS(Trip)) 2]·THF, 8, and [K(PMDTA)S(Trip)]infin;, 9, were synthesized by treatment of HS(Trip) with NaH or KH along with the addition of various donors. The target molecules were characterized by IR, 1H NMR, and depending on solubility, 13C NMR spectroscopy and melting point. Compounds 1-3 and 5-9 were also characterized by single-crystal X-ray crystallography. Analysis of structural data clearly indicates that the structural chemistry of the target molecules can be influenced by donor choice, as exemplified by the large structural diversity observed in the target molecules; the use of a crown ether allowed the isolation of the monomeric species 5, whereas the use of a monodentate donor, such as THF, led to the isolation of the ladder-type polymer 7 or the discrete hexameric compounds 2 and 6. Addition of the bidentate donor TMEDA to a solution of [NaS(Trip)]infin; resulted in the formation of the one-dimensional zigzag polymer 3, whereas utilization of the tridentate donor PMDTA allowed the isolation of the dimer 1. Changing from sodium to potassium and utilization of the tridentate donor PMDTA yielded the one-dimensional zigzag polymer 9, while employment of a mixture of mono- and bidentate donors (THF and TMEDA) resulted in the asymmetrically coordinate hexamer 8. Crystal data with Mo Kα (λ = 0.71073 Å) at 150 K are as follows: 1, a = 13.2300(1) Å, b = 10.6176(1) Å, c = 19.6262(3) Å, β = 100.449(1)°, V = 2711.19(5) Å3, Z = 4, monoclinic, space group P21/n, 6309 independent reflections, R1 (all data) = 0.1004; 2, a = 14.4178(3) Å, b = 17.6498(4) Å, c = 26.2052(6) Å, α = 89.847(1)°, β = 77.475(1)°, γ = 70.189(1)°, V = 6106.3(2) Å3, Z = 2, triclinic, space group P1̄, 25 722 independent reflections, R1 (all data) = 0.1311; 3, a = 9.2702(1) Å, b = 20.1017(2) Å, c = 25.9256(4) Å, V = 4831.15(10) Å3, Z = 8, orthorhombic, space group Pbca, 5032 independent reflections, R1 (all data) = 0.1125; 5, a = 14.196(3) Å, b = 15.429(3) Å, c = 22.562(5) Å, α = 101.92(2)°, β= 97.31(3)°, γ = 114.19(3)°, V = 4313(2) Å3, Z = 4, triclinic, space group P1̄, 6592 (I > 2σ(I)) data, R = 0.074; 6, a = 15.071(3) Å, b = 25.301 (5) Å, c = 17.866(4) Å, β = 113.01(3)°, V = 6270(3) Å3, Z = 2, monoclinic, space group P21/n, 2332 (I > 2σ(I)) data, R = 0.103; 7, a = 11.9079(2) Å, b = 14.7672(2) Å, c = 24.0448(1) Å, β = 98.220(1)°, V = 4184.75(9) Å3, Z = 4, monoclinic, space group P21/c, 9693 independent reflections, R1 (all data) = 0.1324; 8, a = 18.324(4) Å, b = 14.323(3), c = 26.300(5) Å, β = 106.39(3)°, V = 6622(3) Å3, Z = 2, monoclinic, space group P21/c, 4511 (I > 3σ(I)) data, R = 0.105; 9, a = 10.4903(2) Å, b = 20.1551(5) Å, c = 26.4295(4) Å, V = 5588.1(2) Å3, Z = 8, orthorhombic, space group Pbca, 6649 independent reflections, R1 (all data) = 0.146.
AB - The synthesis and characterization of a family of sodium and potassium thiolates [A(donor)S(Trip)]2 (A = Na, K; Trip = 2,4,6-i-Pr3C6H2, n = 1-∞) is described. [Na(PMDTA)S(Trip)]2, 1 (PMDTA = N,N,N′,N″,N″-pentamethyldiethylenetriamine), [(NaS(Trip))2(Na(Et2O)S(Trip))4]·0.5 solvent, 2, [Na(TMEDA)S(Trip)]infin;, 3 (TMEDA = N,N,N′,N′-tetramethylethylenediamine), [Na(THF)S(Trip)]n, 4 (n = 6 or ∞), [K(dibenzo-18-crown-6)(THF)S(Trip)]·THF, 5, [(KS(Trip))2(K(THF)S(Trip))2(K(THF) 2S(Trip))2], 6, [K(THF)S(Trip)]infin;, 7, [(K(THF)S(Trip))2(K(TMEDA)S(Trip))2(KS(Trip)) 2]·THF, 8, and [K(PMDTA)S(Trip)]infin;, 9, were synthesized by treatment of HS(Trip) with NaH or KH along with the addition of various donors. The target molecules were characterized by IR, 1H NMR, and depending on solubility, 13C NMR spectroscopy and melting point. Compounds 1-3 and 5-9 were also characterized by single-crystal X-ray crystallography. Analysis of structural data clearly indicates that the structural chemistry of the target molecules can be influenced by donor choice, as exemplified by the large structural diversity observed in the target molecules; the use of a crown ether allowed the isolation of the monomeric species 5, whereas the use of a monodentate donor, such as THF, led to the isolation of the ladder-type polymer 7 or the discrete hexameric compounds 2 and 6. Addition of the bidentate donor TMEDA to a solution of [NaS(Trip)]infin; resulted in the formation of the one-dimensional zigzag polymer 3, whereas utilization of the tridentate donor PMDTA allowed the isolation of the dimer 1. Changing from sodium to potassium and utilization of the tridentate donor PMDTA yielded the one-dimensional zigzag polymer 9, while employment of a mixture of mono- and bidentate donors (THF and TMEDA) resulted in the asymmetrically coordinate hexamer 8. Crystal data with Mo Kα (λ = 0.71073 Å) at 150 K are as follows: 1, a = 13.2300(1) Å, b = 10.6176(1) Å, c = 19.6262(3) Å, β = 100.449(1)°, V = 2711.19(5) Å3, Z = 4, monoclinic, space group P21/n, 6309 independent reflections, R1 (all data) = 0.1004; 2, a = 14.4178(3) Å, b = 17.6498(4) Å, c = 26.2052(6) Å, α = 89.847(1)°, β = 77.475(1)°, γ = 70.189(1)°, V = 6106.3(2) Å3, Z = 2, triclinic, space group P1̄, 25 722 independent reflections, R1 (all data) = 0.1311; 3, a = 9.2702(1) Å, b = 20.1017(2) Å, c = 25.9256(4) Å, V = 4831.15(10) Å3, Z = 8, orthorhombic, space group Pbca, 5032 independent reflections, R1 (all data) = 0.1125; 5, a = 14.196(3) Å, b = 15.429(3) Å, c = 22.562(5) Å, α = 101.92(2)°, β= 97.31(3)°, γ = 114.19(3)°, V = 4313(2) Å3, Z = 4, triclinic, space group P1̄, 6592 (I > 2σ(I)) data, R = 0.074; 6, a = 15.071(3) Å, b = 25.301 (5) Å, c = 17.866(4) Å, β = 113.01(3)°, V = 6270(3) Å3, Z = 2, monoclinic, space group P21/n, 2332 (I > 2σ(I)) data, R = 0.103; 7, a = 11.9079(2) Å, b = 14.7672(2) Å, c = 24.0448(1) Å, β = 98.220(1)°, V = 4184.75(9) Å3, Z = 4, monoclinic, space group P21/c, 9693 independent reflections, R1 (all data) = 0.1324; 8, a = 18.324(4) Å, b = 14.323(3), c = 26.300(5) Å, β = 106.39(3)°, V = 6622(3) Å3, Z = 2, monoclinic, space group P21/c, 4511 (I > 3σ(I)) data, R = 0.105; 9, a = 10.4903(2) Å, b = 20.1551(5) Å, c = 26.4295(4) Å, V = 5588.1(2) Å3, Z = 8, orthorhombic, space group Pbca, 6649 independent reflections, R1 (all data) = 0.146.
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U2 - 10.1021/ic970769l
DO - 10.1021/ic970769l
M3 - Article
AN - SCOPUS:0001032679
SN - 0020-1669
VL - 37
SP - 283
EP - 293
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 2
ER -