Schwermetall‐π‐Komplexe. X. Synthese und Kristallstruktur von {[(1,3,5‐(CH₃)₃C₆H₃)₂Tl][AlCl₄]}₂: ein arenstabilisiertes dimeres Thallium(I)‐tetrachloroaluminat

Abstract

Aus einer Lösung von AlCl3 und TlCl in Mesitylen kristallisiert bei tiefen Temperaturen der Bis(aren)‐thallium(I)‐Komplex {[(1,3,5‐(CH3)3C6H3)2Tl][AlCl4]}2 (1) (Raumgruppe P21/c mit a = 19,575(4) Å, b = 12,436(2) Å, c = 19,415(4) Å, β = 101,69(3)° bei T = −90 ± 1°C; Z = 4). Die Verbindung kann als dimeres Thallium(I)‐tetrachloroaluminat mit (TeI4)4‐ähnlichem Gerüst aufgefaßt werden, das durch eine Solvathülle aus vier paarweise an die Tl‐Atome gebundenen Arenmolekülen stabilisiert wird. Im Kristall weist die gesamte Anordnung lediglich die Punktsymmetrie 1 (C1) auf. TlCl‐Abstände von 3,292(3)–3,679(3) Å deuten auf eine ionische Bindungsbeziehung zwischen Aren2Tl+‐ und AlCl4−‐Fragmenten hin. Die Stärke der η6‐ähnlichen Tl‐Aren‐Wechselwirkungen wird durch die Abstände Tl(1)–C von 3,250 Å bzw, 3,315 Å und Tl(2)–C von 3,285 Å bzw. 3,328 Å und eine differentialthermoanalytisch bestimmte Abgabetemperatur aller Arenmoleküle von 61°C unter Bildung phasenreinen Thallium(I)‐tetrachloroaluminats charakterisiert.

Tl(I)-, Cu(I)-, and Ag(I) Complexes of the Ditopic 1,3-Phenylene-Bridged Heteroscorpionate Ligand [1,3-C6H4(tBuBpz2)2]2-

“…and fall in the same range as in other Tl(I)-arene complexes 19,[26][27][28][29]. Recently, a novel coordination geometry of thallium(I) tris(pyrazol-1-yl)borate complexes has been discovered in polymeric [(FcBpz 3 )Tl] n 5,30 (Fc ) (C 5 H 5 )Fe(C 5 H 4 )), in [(CymBpz 3 )Tl] 4 31 (Cym ) (MeC 5 H 3 )-Mn(CO) 3 ), which forms cyclic tetramers, and in the monomeric species [(PhBpz tBu 3 )Tl] 22.…”

“…These values are consistent with the Tl−N bond lengths and N−Tl−N bond angles reported previously for some mononuclear thallium bis(pyrazol-1-yl)borate compounds. − In complexes of the type [(H 2 Bpz 2 )Tl], the bonding to the “two-coordinate” Tl(I) ions is usually augmented by a weak intramolecular B−H···Tl interaction. ,, In the case of 1Tl , however, a third Tl coordination site is occupied by the respective ipso -carbon atom of the phenylene core (Figure ). The corresponding distances Tl(1)···C(51) = 3.02 Å and Tl(2)···C(53) = 3.03 Å are significantly shorter than the sum of the van der Waals radii (3.66 Å) of thallium (1.96 Å) and carbon (1.70 Å) 25 and fall in the same range as in other Tl(I)-arene complexes. ,− Recently, a novel coordination geometry of thallium(I) tris(pyrazol-1-yl)borate complexes has been discovered in polymeric [(FcBpz 3 )Tl] n , (Fc = (C 5 H 5 )Fe(C 5 H 4 )), in [(CymBpz 3 )Tl] 4 (Cym = (MeC 5 H 3 )Mn(CO) 3 ), which forms cyclic tetramers, and in the monomeric species [(PhBpz t Bu 3 )Tl] . In these three compounds the Tl(I) ion forms σ-adducts with only two of the scorpionate's pyrazolyl groups, while the third pyrazolyl ring is rotated by approximately 90° about the B−N bond.…”

Unusual Coordination Behavior of Pn‐Ligand Complexes with Tl+

“…[12] Only a few additional examples have since been published. [13] À ) exist. [11] The absence of interactions with the counterion facilitates the investigation of the coordination behavior of the free Tl + ion.…”

π-Complexation of Post-Transition Metals by Neutral Aromatic Hydrocarbons: The Road from Observations in the 19th Century to New Aspects of Supramolecular Chemistry

“…Each Tl + cation is also η 6 -coordinated by two mesitylene molecules at Tl−ring plane distances in the narrow range from 2.93 to 3.02 Å and with angles between the ring planes of 50.8 and 54.4° ( 10 ). According to DTA studies, the compound loses mesitylene at 61 °C …”