Agostic Pd ⋯ H⁺⋯ NHR₂and apical Pd ⋯ NHR₂interactions: the synthesis and structures of [Pd^IICl₂(H[9]aneN₃)]⁺, the Pd^II–Pd^IIdimer [(H[9]aneN₃)Cl₂Pd–PdCl₂(H[9]aneN₃)]²⁺, and [Pd(Me₃[9]aneN₃)(NCMe)₂]²⁺

Reduction of Water to H2 by Diorganopalladium(II) Complexes of Tris(pyrazol-1-yl)borate: Ab-Initio Theoretical Study of the Mechanism

“…Several platinum(IV) hydrides have been obtained by protonation of Pt(II) complexes, 2d,,− including those for tripod nitrogen donor ligands. 2d,, In one case, which is of particular interest here since it involves [(pz*) 3 BH] - (pz* = 3,5-Me 2 pz) as a ligand, an X-ray crystal structure has been obtained . N-protonated Pt(II) complexes are also known. ,,26a,− In the case of palladium, N-protonated Pd(II) complexes have been characterized 26,27 but to our knowledge organo(hydrido)palladium(IV) species have not been fully characterized . Calculations that we reported recently showed that for the protonation of the [PtMe 2 {(H 2 CN NH) 3 BH}] - model system, the Pt(IV) hydride was more stable than the N-protonated species by about 22 kcal mol -1 …”

Dinuclear Palladium(III) Complexes with a Single Unsupported Bridging Halide Ligand: Reversible Formation from Mononuclear Palladium(II) or Palladium(IV) Precursors

“…[8] While triazacyclonane (tacn) [9,10] and other tacn derivatives [11] have been employed in the synthesis of Pd complexes, only one complex, [(Me 3 tacn)Pd II (MeCN) 2 ](PF 6 ) 2 , has been reported for Me 3 tacn. [10] We have synthesized the Pd .…”

“…In addition, the reported Pd III systems are the first group 10 d 7 -d 7 dinuclear complexes bridged by a single unsupported halide ligand and represent a model of the delocalized Pd III ÀXÀPd III electronic structure that has been proposed to exist in some ÀPdÀXÀPdÀXÀ one-dimensional (1D) chains. [8] While triazacyclonane (tacn) [9,10] and other tacn derivatives [11] have been employed in the synthesis of Pd complexes, only one complex, [(Me 3 tacn)Pd II (MeCN) 2 ](PF 6 ) 2 , has been reported for Me 3 tacn. [10] We have synthesized the Pd II complexes [(Me 3 tacn)Pd II X 2 ] (X = Cl 1 a, X = Br 1 b) through the reaction of Me 3 tacn with [(MeCN) 2 Pd II X 2 ].…”

“…[8] While triazacyclonane (tacn) [9,10] and other tacn derivatives [11] have been employed in the synthesis of Pd complexes, only one complex, [(Me 3 tacn)Pd II (MeCN) 2 ](PF 6 ) 2 , has been reported for Me 3 tacn. [10] We have synthesized the Pd II complexes [(Me 3 tacn)Pd II X 2 ] (X = Cl 1 a, X = Br 1 b) through the reaction of Me 3 tacn with [(MeCN) 2 Pd II X 2 ]. [12] The X-ray structure analysis of 1 a reveals a square-planar arrangement of two Cl À ions and two N atoms around Pd, while the third N atom of Me 3 tacn is not in close proximity to the metal center (Figure 1 a), [13] in contrast to the five-coordinate geometry observed for [(Me 3 tacn)Pd II (MeCN) 2 ](PF 6 ) 2 .…”

“…[12] The X-ray structure analysis of 1 a reveals a square-planar arrangement of two Cl À ions and two N atoms around Pd, while the third N atom of Me 3 tacn is not in close proximity to the metal center (Figure 1 a), [13] in contrast to the five-coordinate geometry observed for [(Me 3 tacn)Pd II (MeCN) 2 ](PF 6 ) 2 . [10] Cyclic voltammetry (CV) of both 1 a and 1 b in MeCN/Bu 4 NPF 6 reveals two closely-spaced waves at 0.05-0.17 V versus Fc + /Fc and additional waves at higher potentials, suggestive of oxidatively induced chemical reactions. [12,14] Controlled potential electrolysis (CPE) at 0.3-0.4 V for both 1 a and 1 b leads to formation of a dark purple species in 60-70 % yields of isolated product after passing a charge corresponding to a one-electron oxidation.…”