Quantification of cis and trans influences in [PtX(PPh3)3]+ complexes. A 31P NMR study

Trans and cis influences and effects in cobalamins and in their simple models

“…For example, a previous study by Burgi et al [18] on cobaloximes revealed that both axial distances lengthen when the electron donating ability of the X group increases. This behavior was called inverse trans influence, in contrast to the normal trans influence, which occurs when the lengthening of one axial bond corresponds to a shortening of the other [1][2][3][4][5][6][7][8]. On the basis of a careful reanalysis of the available data of the axial fragment, we provide here new evidence that both normal and inverse trans influences occur in cobaloximes.…”

“…The ability of a ligand to affect the metal-ligand bond of another ligand can be exerted electronically, by direct transmission through the metal (electronic influence), or sterically, by nonbonding interactions between the ligands (steric influence). The assignment of electronic or steric effects/influences allows rationalization of important properties of square planar [2,3] and octahedral [4][5][6][7][8] transition metal complexes, such as geometry, stability, and reactivity. Generally, the terms cis effect and trans effect refer to kinetics, whereas cis and trans influence refers to ground state and thermodynamic properties.…”

“…In general, the interpretation of such mutual ligand interactions in terms of steric and electronic properties of the ligands (cis and trans influences and effects) [5][6][7][8][10][11][12][13] is not a trivial matter because the electronic and steric effects of a ligand are often superimposed. Nevertheless, several attempts to quantify [11,12] and to separate their contributions have been carried out [2,3,13].…”

The Trans Influence in Unsymmetrical Pincer Palladacycles: An Experimental and Computational Study

“…The trans influence has been used to explain the stability of square planar complexes [24], while the trans effect has been used to study reaction pathways [25]. There are many experimental studies into the trans influence, generally using spectroscopic or X-ray crystallographic methods [26][27][28]. Additionally, density functional theory (DFT) structure optimization and molecular orbital analysis have been employed in the study of the Figure 1.…”

Tin(II) Halide Insertion or Halogen Exchange in the Reactions of Dihaloplatinum(II) Complexes with Tin(II) Halide

“…The following reagents were used as supplied: dppf (Aldrich), dppm (Merck), dppe (Merck), dppp (Merck), dppb (Acros), and dpppe (Alfa Aesar). 31 2 ] and cis-[PtCl 2 (P 2 )] (P ¼ Ph 3 P and (MeO) 3 P; P 2 ¼ dppm (see 9), dppe (see 11), and dpppe (see 4)) were prepared as described in [2] [35], and cis-[PtBr 2 (Ph 3 P) 2 ] (c-23) [24] were prepared in good yield by metathesis of cis-[PtCl 2 (P 2 )] with two equiv. of KX (X ¼ Br, I) in acetone.…”