Affiliations: Technische Universität München, Anorganisch-chemisches Institut, Lichtenbergstr. 4, 85747 Garching, Germany | Department of Chemistry, University of Delaware, Newark, Delaware 19716, USA
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Abstract: The molecular structures of three different base-adducts of a potassium salt of an asymmetrically substituted phosphane [i.e., HP(tBu)Ph] are reported. They feature onedimensional polymeric ladder-type connectivities of potassium and phosphorus atoms in the solid-state. Reaction of KH with HP(tBu)Ph (1) in tetrahydrofuran at room temperature gives KP(tBu)Ph (2) in 60% yield. 2 was crystallized from hexane/tetrahydrofuran, toluene/N-methylimidazole, and also from toluene/pyridine yielding {[KP(tBu) Ph]2·(tetrahydrofuran)}x, (3), {[KP(tBu)Ph]2·(N-methylimidazole)}x (4), and {[KP(tBu)Ph]2·(pyridine)}x (5), respectively. 3 crystallizes in spage group P1. Crystal data for 3 at 203 K: a = 11.1698 (4) Å; b = 12.4434 (5) Å; c = 22.7545 (8) Å; α = 91.0100(10)°; β = 93.6230 (10)°; γ = 114.4250(10)°; V = 2870.5 (2) Å3; Z = 2; Dcalcd = 1.112 g cm−3; RF = 9.77%. 4 crystallizes in space group P21/n. Crystal data for 4 at 223 K: a = 12.9256 (2) Å; b = 11.23380 (10) Å; c = 20.2498 (2) Å; β =97.0560 (10)° V = 2918.08 (6) Å3; Z=4; Dcalcd = 1.117 g cm−3; RF = 4.96%. 5 crystallizes in space group P1. Crystal data for 5 at 293 K: a = 12.2688 (2) Å; b = 12.4773 (2) Å; c = 19.1916 (2) Å; α = 91.5930 (10)°; α = 92.1270(10)°; γ = 94.0860 (10)°; V = 2927.03 (7) Å3;Z = 4; Dcalcd = 1.107 g cm−3; RF =6.17%. A main feature of complexes 3 – 5 are infinitely extended polymeric one-dimensional K-P ladder-type connectivities of the type AA′BB′AA′BB′. Different coordination environments are found to be present for the potassium cations in 3 – 5. 31P MAS and 13C CP/MAS NMR data for KP(tBu)Ph (2) are presented.
