How Cationic Metalloligands Affect the Coordination of Lewis Basic Ligands in Rh^IComplexes

Abstract

A series of Rh I complexes featuring cationic diphosphinometal ligands (PMP n+ ) has been synthesized, and the effect of the dative Rh I → M n+ interactions on other ligands coordinated to the Rh I center were studied. The Rh−CO bond strength in square pyramidal [(PMP)Rh(CO)X] n+ -type complexes (X = Cl, H) is dominated by the charge of the metalloligand. Complex [(PZnP)Rh(CO)H](NTf 2 ) 2 ( 7) was evaluated for its competence in hydroformylation catalysis. Computational analysis of octahedral [(PMP)Rh(CO) 2 H] n+ model complexes revealed a strengthening of the Rh−CO bond trans to the metalloligand with increasing atomic number of the metalloligand.

The dn Number in Transition Metal Chemistry: Its Utility and Limitations

“…[60] in relation to [Mo(η 7 -C 7 H 7 )(CO) 3 ] + (9 in Figure 2), where it was argued that since this species displays tropylium-like chemistry for the C 7 H 7 ligand, a [C 7 H 7 ] + assignment is preferred leading to a d 6 configuration for 9 rather than the d 2 configuration derived using the CBC method. Cationic ligands are not common, but many examples are nevertheless known (in addition to [NO] + and [C 7 H 7 ] + ) for which the assignment of a d n number using the OS method is generally straightforward [72][73][74][75][76]. However, it is important to recognise that the CBC method treats cationic ligands rather differently since, in general, an L + designation transforms to X according to Scheme 1 (i), which then has consequences for the assignment of a d n number (Appendix A Note 26).…”

The heterometallic one-dimensional solvated coordination polymer [NiPt2Cl6(TRIP-Py)4] n

“…In this article, we address the selectivity of a soft phosphorus and a harder nitrogen donor. This combination has been demonstrated to give selective heterometallic coordination compounds for a long list of discrete metal complexes (Hara et al, 2021;Schroers et al, 2021). In CP chemistry, however, the same pair of donor sites has only very recently been used for a heterometallic CP (Gildenast et al, 2022a).…”

Phosphorus or nitrogen – the first phosphatriptycene in coordination polymer chemistry

“…That this combination can display selectivity has been demonstrated numerous times in discrete bimetallic complexes. [41][42][43][44] There are even quite a few examples of P,N heteroditopic ligands that form coordination polymers, however, all of these were monometallic CPs. [45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60][61][62][63][64] With our ligand design we want to adhere as closely as possible to the key principals mentioned above which is straightforward for the N donor by choosing a pyridine moiety.…”

“…That this combination can display selectivity has been demonstrated numerous times in discrete bimetallic complexes. 41–44 There are even quite a few examples of P,N heteroditopic ligands that form coordination polymers, however, all of these were monometallic CPs. 45–64…”