Die Kristallstruktur des β‐Palladium(II)‐jodids

Abstract

Es wird uber die Darstellung der drei Modifikationen von PdJz berichtet. P-PdJz kristallisiert monoklin (a = 6.69; b = 8.60; c = 6.87A; P = 103.5') in der Raumgruppe P2l/c-C&. In einer verzerrten kubisch dichtesten Packung der Jodatome sind alle Zwischenschichten zur Halfte besetzt. Ebene Pd~Js-Einheiten sind zu gewellten Schichten verkniipft; die Bindung zwischen den Schichten wird durch zwei Jodatome bewirkt, die die Koordination des Pd zu einem gestreckten Oktaeder erganzen.

Bis(benzonitrile)palladium(II) Dihalides: Structures and Cocrystallization of the Cubic Cluster Pd6Cl12 with (E)-Stilbene and with Bis(benzonitrile)palladium(II) Dichloride

“…The solid-state structure of palladium(II) dibromide has been shown to consist of infinite linear chains, ···PdBr 2 PdBr 2 ···, that are similar to the chains seen in α-PdCl 2 . Several polymorphs of PdI 2 are known; the β-phase has a complex structure consisting of planar Pd 2 I 6 units . However, solid phases containing the discrete clusters Pd 6 Br 12 and Pd 6 I 12 are, to our knowledge, unknown, whereas the series of clusters Pd 6 Cl 12 - n Br n where n = 1−12 has been detected in the gas phase from vaporization of mixtures of PdCl 2 and AgBr .…”

“…8 Several polymorphs of PdI 2 are known; the β-phase has a complex structure consisting of planar Pd 2 I 6 units. 9 However, solid phases containing the discrete clusters Pd where n ) 1-12 has been detected in the gas phase from vaporization of mixtures of PdCl 2 and AgBr. 10 The analogous cubic platinum clusters, Pt 6 Cl 12 and Pt 6 Br 12 , have been isolated, 11,12 but their ability to cocrystallize with organic molecules has not been explored.…”

Characterization and Reactivity of the Tetrametallic Pd2-Mo2 Complex Ph(Bu)P(η5-C5H4)Mo(CO)3Pd(μ-I)2PdMo(CO)3(η5-C5H4)P(Ph)Bu and Its Use to Model Pd-Catalyzed Cross-Coupling Reactions Leading to M−C⋮C Bonds

“…The Mo−Pd distance is 2.79 Å (Table ) and is consistent with a single metal−metal bond; the Pd−Pd distance is 3.89 Å, which excludes any bonding interaction between the two metal centers . The structure exhibits a crystallographic center of symmetry at the midpoint between the bridging iodides.…”

“…In contrast, severe distortions affect the P−Pd−Mo−Cp cycle, likely due to the strong Pd−Mo and Pd−P bonds (Table ) and to the steric pressure of the CO ligands. Indeed, the P1−Pd1−I1‘ (177.5°) and P1−Pd1−I1 (93.5°) angles deviate appreciably from the ideal values, while the Pd1−I1‘ and Pd1−I1 distances, (2.72 and 2.67 Å, respectively) are longer than those reported for similar systems devoid of surrounding bulky ligands. 14a,15c Moreover, the Cp centroid −Mo1−Pd1 angle measures only 110.7°, while the Cp centroid −Mo1−C1, the Cp centroid −Mo1−C2, and the Cp centroid −Mo1−C3 angles are significantly larger (122.9°, 125.1°, and 125.8°, respectively). The steric influence of the CO groups on the bridging iodines is made evident by the deviation from linearity of the Mo−C−O bonds.…”