| Abstract: | Synthesis and Crystal Structure of the Complexes (n‐Bu)4N]2{(THF)Cl4Re≡N}2PdCl2], Ph4P]2(THF)Cl4Re≡N‐PdCl(μ‐Cl)]2 and (n‐Bu)4N]2Pd3Cl8] The threenuclear complex (n‐Bu)4N]2{(THF)Cl4Re≡N}2 PdCl2] ( 1 ) is obtained in THF by the reaction of PdCl2(NCC6H5)2 with (n‐Bu)4N]ReNCl4] in the molar ration 1:2. It forms orange crystals with the composition 1· THF crystallizing in the monoclinic space group C2/c with a = 2973.3(2); b = 1486.63(7); c = 1662.67(8)pm; β = 120.036(5)° and Z = 4. If the reaction is carried out with PdCl2 instead of PdCl2(NCC6H5)2, orange crystals of hitherto unknown (n‐Bu)4N]2Pd3Cl8] ( 3 ) are obtained besides some crystals of 1· THF. 3 crystallizes with the space group P1¯ and a = 1141.50(8), b = 1401.2(1), c = 1665.9(1)pm, α = 67.529(8)°, β = 81.960(9)°, γ = 66.813(8)° and Z = 2. In the centrosymmetric complex anion {(THF)Cl4Re≡N}2PdCl2]2— a linear PdCl2 moiety is connected in trans arrangement with two complex fragments (THF)Cl4Re≡N]— via asymmetric nitrido bridges Re≡N‐Pd. For Pd(II) thereby results a square‐planar coordination PdCl2N2. The linear nitrido bridges are characterized by distances Re‐N = 163.8(7)pm and Pd‐N = 194.1(7)pm. The crystal structure of 3 contains two symmetry independent, planar complexes Pd3Cl8]2— with the symmetry 1¯, in which the Pd atoms are connected by slightly asymmetric chloro bridges. By the reaction of equimolar amounts of Ph4P]ReNCl4] and PdCl2(NCC6H5)2 in THF brown crystals of the heterometallic complex, Ph4P]2(THF)Cl4Re≡N‐PdCl(μ‐Cl)]2 ( 2 ) result. 2 crystallizes in the monoclinic space group P21/n with a = 979.55(9); b = 2221.5(1); c = 1523.1(2)pm; β = 100.33(1)° and Z = 2. In the central unit ClPd(μ‐Cl)2PdCl of the centrosymmetric anionic complex (THF)Cl4Re≡N‐PdCl(μ‐Cl)]22— the coordination of the Pd atoms is completed by two nitrido bridges Re≡N‐Pd to nitrido complex fragments (THF)Cl4Re≡N]— forming a square‐planar arrangement for Pd(II). The distances in the linear nitrido bridges are Re‐N = 163.8(9)pm and Pd‐N = 191.5(9)pm. |
