Iodoplumbate mit polymeren Anionen – Synthese und Kristallstrukturen von [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)], (Ph₄P)₂[Pb₅I₁₂] und (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆]

Abstract

Inhaltsiibersicht. Bei Umsetzungen von Pb12 mit NaI in polaren organischen Losungsmitteln entstehen Iodoplumbatkomplexe unterschiedlicher Zusammensetzungen und Strukturen, die durch Kristallisation mit groRen Kationen isoliert werden konnen. [Na3(OCMez)121[Pb41,,(OCMe2)1 3, (Ph4P)2[Pb511~I 4 und (Ph4P)4[Pb15134(dmf)6] 7 enthalten eindimensional unendliche Anionen, die aus flachen-bzw. kantenverknupften Pb1,-oder PbI&Oktaedern (L = Aceton, DMF) aufgebaut sind.[Na3(OCMe2),2][Pb4111(OCMe2)] 3: Raumgruppe PI (Nr. I), a = 1120,3(5), b = 1265,3(6), c = 1608,3(8)pm, 01 = 74,64(4), p = 70,40(4), y = 85,24(4)", V = 2071(2) * 106pm3;(Ph4P),[Pb5112] 4: Raumgruppe C2/c (Nr. 15), a = 787,00(10), b = 2812,0(5), c = 3115,9(5) pm, p = 96,240 (13)", V = 6885(2) . 106pm3; (Ph,P),[Pbi51~4(dmf)6] 7: Raumgruppe P2Jn (Nr. 14), a = 2278,8(4), b = 1782,6(3), c = 2616,8(4) pm, / 3 = 114,432(13)", V = 9678(3) * 106pm3. Abstract. Reactions of PbIz with NaI in polar organic solvents followed by crystallization with large cations yield iodoplumbate complexes with various compositions and structures. [Na3(OCMe2)lzl [Pb4111(OCMe2)1 3, (Ph4P)2[Pb51121 4 and (Ph4P)4[Pb15134(dmf>6] 7 contain one-dimensional infinite anionic chains of face-or edge-sharing Pb16 or Pb15L (L = acetone, DMF) octahedra. [Na3(OCMe2)12] [Pb411,(OCMe2)] 3: Space group PI (No. I), a = 1120.3(5), b = 1265.3(6), c = 1608.3(8) pm, 01 = 74.64(4), p = 70.40(4), y = 85.24(4)", V = 2071(2) . 106pm3; (Ph4P)2[Pb511z] 4: Space group C2/c (No. 15), a = 787.00(10), b = 2812.0(5), c = 3115.9(5) pm, p = 96.240(13)", V = 6885(2) * 106pm3; (Ph4P)4[Pb15134(dmf)6] 7: Space group P2,/n (No. 14), a = 2278.8(4), b = 1782.6(3), c = 2616.8(4)pm, p = 114.432(13)", V = 9678(3) -106pm3.

1D and 2D Polybromotellurates(IV): Structural Studies and Thermal Stability

“…Synthesis in conc. HBr (acting both as solvent and the source of bromide ligands) resulted in the structures based solely upon [TeBr 6 ] 2– , and this fact agrees with general observations on halotellurate chemistry: unlike Pb II , Sb III , or Bi III , Te IV prefers mononuclear species if the halide ligand is in excess. Despite our expectations that the use of other cations might promote aggregation of {TeBr 6 } into more sophisticated moieties, it did not occur in 1 – 3 ; there are only mononuclear units connected via {Br 2 } in different modes.…”

Halide-bridged polymers of divalent metals with donor ligands – structures and properties

“…In the latter, face-sharing hexaiodoplumbate and acetone-pentaiodoplumbate moieties are arranged in 3:1 stoichiometry (Fig. 34); the donor-ligand acetone is "diluted" along the anionic chains [166] which at the same time provide an example for the rarely encountered face-sharing of octahedra. The Pb· · ·Pb distance between cations sharing a common face amounts to 4.047 Å.…”

“…With tetraphenylphosphonium counter cations, an anionic ribbon with the repeat unit [Pb 15 I 34 (dmf) 6 ] 4− was crystallized [166]; this composition is obtained from five [M 3 X 6 L 2 ] units when four of the donor ligands L in the resulting [M 15 X 30 L 10 ] are replaced by halides X − . A segment of the polyanion is shown in Fig.…”

Polymere Iodoplumbate - Synthese und Kristallstrukturen von (Pr3N-C2H4-NPr3)[Pb6I14(dmf)2] · 4 DMF, (Pr3N-C2H4-NPr3)[Pb(dmf)6][Pb5I14] · DMF und (Me3N-C2H4-NMe3)2[Pb2I7]I

“…Nach diesem Syntheseprinzip entstehen (Bu 4 N) 8 [6]. In beiden Verbindungen be-finden sich die I-Atome und die O-Atome der DMF-Liganden in zwei zueinander parallelen Ausschnitten dichtest gepackter Schichten.…”

“…Pb3 0,25351 (6) 0,21424(4) 0,66002(4) 0,0334 (2) Pb4 0,75780 (6) 0,22585(4) 0,65117(4) 0,0359 (2) I1 0,0334(1) 0,29964 (7) 0,49323 (7) 0,0353 (3) I2 0,2325(1) 0,43636 (7) 0,64990 (7) 0,0361(3) I3 0,2679(1) 0,56805 (7) 0,34540 (7) 0,0373 (3) I4 0,5218(1) 0,29822 (7) 0,49475 (7) 0,0364 (3) I5 ±0,0152(1) 0,18199 (8) 0,80304 (7) 0,0469 (4) (9) 0,882 (2) 0,030 (8) N2 ±0,041 (3) 1,0293 (9) 1,116 (2) 0,024 (7) Pb6 0,88790 (6) (4) …”