Structure of trimethylplatinum(IV) with a tripod ligand

Carbon−Oxygen Bond Formation at Metal(IV) Centers: Reactivity of Palladium(II) and Platinum(II) Complexes of the [2,6-(Dimethylaminomethyl)phenyl-N,C,N]-(Pincer) Ligand toward Iodomethane and Dibenzoyl Peroxide; Structural Studies of M(II) and M(IV) Complexes

“…In the metal(II) complexes, the M−C and M−O distances do not differ nontrivially, but the Pd−N distances are ∼0.02 Å longer than their Pt−N counterparts. These trends are consistent with other reports of isostructural organometal pairs in which Pd−N, P, O, S, and Cl distances are similar to or longer than the Pt analogues. − …”

“…These trends are consistent with other reports of isostructural organometal pairs in which Pd-N, P, O, S, and Cl distances are similar to or longer than the Pt analogues. [21][22][23][24][25] In the triad of Pt(IV) complexes, despite the increase in oxidation state, metal-ligand distances are increased compared with the M(II) complexes, in keeping with the increase in coordination number. The additional carbon atoms bound to the metal in 5 and 7 lie cis to the tridentate, as found for cis-PtI 2 (Tol-4)(NCN).…”

Synthesis and solid-state structural characterisation of Pt(II,IV) bromide complexes containing bidentate organothiomethylpyridine heteroleptic ligands

“…Comparison of the solid state structures of [MCl 2 {2-(PhSCH 2 )C 5 H 4 N}] (M = Pd, Pt) and results from theoretical studies of solution processes indicate that the Pt-S bond is stronger than Pd-S, consistent with the softer Lewis acidity of platinum compared with palladium. Similar trends in bond distances in isomorphous structures of palladium and platinum complexes containing homoleptic and heteroleptic ligands have been observed and theoretical calculations have been performed [12][13][14][15][16].…”

Effects of Trifluoromethyl Substituents in a Tris(pyrazolyl)borate Ligand: A Structural and Spectroscopic Study of Analogous Platinum(IV) Trimethyl Complexes

“…In contrast to the observations for the “N 3 ”PtMe 3 complexes, the Pt−Me coupling constants for “O 3 ”PtMe 3 complexes (11 examples) are generally higher, ranging from 75.7 to 81.6 Hz with an average value of 79.6 Hz. ,,,17b,24a As shown in Figure , there is a good correlation between the 2 J Pt - H coupling constants and the crystallographically determined Pt IV −C bond lengths for a series of “D 3 ”PtMe 3 complexes (D = donor group). As expected, it is an inverse relation such that longer Pt IV −C bonds are associated with lower values of 2 J Pt - H .…”

“…However, as discussed below, the Pt−H and Pt−C coupling constants observed by NMR are also supportive of longer Pt−C bonds in 2 . It is also interesting to compare the Pt−C bond lengths in 1 and 2 to those in other “N 3 ”PtMe 3 complexes in which a typical bond length appears to be about 2.06 Å (see Table S1 in the Supporting Information). 9d,− However, the average Pt−C bonds in analogous Pt(IV) trimethyl complexes with tripodal oxygen donor ligands are in general shorter (2.00−2.04 Å, Table S1). ,− These differences between the Pt−C bond lengths in the nitrogen-ligated and oxygen-ligated complexes listed are consistent with the differences in the expected trans influences of the ligands . It is reasonable that the fluorination of the nitrogen-based hydridotris(dialkylpyrazolyl)borate ligand should reduce its donor ability and so lead to a reduction in its trans influence.…”