Synthesis and characterization of palladium complex trans-(Me3P)2Pd(C6H4C(H):NPr-iso)(NHPh). X-ray crystal structure analysis of [(Me3P)3Pd(C6H4C(H):NPr-iso)][BF4]

Cyclometallated complexes derived from pyrimidin- and pyridazinehydrazones: Structural evidence of intermolecular “chelate metal ring” π–π interactions

“…The Pd(1)-N(1) distance of 2.410(3) and 2.448(3) Å for 7a and 7b, respectively, is somewhat longer than the values of 2.338(3) Å, reported recently by us in a similar complex with a triphos ligand [29], and of 2.23(2) Å found in an authentic pentacoordinated palladium(II) complex [58]. However, the Pd-N bond length is shorter than the weak interactions in the range 2.576(4)-2.805(5) Å found in other five-coordinated complexes of palladium [59][60][61][62][63][64]. The s parameter, an index of trigonality [65] as a general descriptor of five-co-ordinate molecules, is 0.63 and 0.42, for complexes 7a and 7b, respectively, nearly half-way between the trigonal-bipyramidal (s = 1) and the square pyramidal (s = 0) geometry; therefore, coordination around the palladium atom may be viewed as a distorted trigonal-bipyramid, with the Pd(1), N(1), P(1) and P(3) atoms in the equatorial plane and the metallated carbon atom and the central phosphorus atom at the apical position, or alternatively it may be regarded as square pyramidal with the Pd(1), C(1), P(1), P(2) and P(3) atoms in the basal plane and the nitrogen at the apical position (see Tables 3-5).…”

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

“…A constrained C s geometry optimization with the H 2 CNNH group above the palladium atom yielded 1a , where the Pd···N distance is 3.48 Å. This is clearly indicative of no interaction: typical Pd···N(sp 2 ) weak interactions are characterized by a distance of 2.7−2.8 Å …”

Experimental and Computational Study of the Bonding Properties of Mixed Bis−Ylides of Phosphorus and Sulfur

“…This means that 12 is obtained as two geometric isomers, in which the phosphine is bonded either trans to the aryl ring or trans to the ylidic carbon. Even if the PPh 3 ligand is reluctant to coordinate trans to an aryl ligand, a phenomenon known as transphobia , and based on the antisymbiotic effect, there are some reports in which this situation is postulated or crystallographically characterized. − On these grounds, we have assigned the PPh 3 trans to C ylide structure to the major isomer because this should be the most favorable arrangement. These spectra also show unambiguously the presence of the orthometalated unit.…”